Carbon-Based Materials

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Metal-supported carbon-based materials:

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opportunities and challenges in the synthesis of

Cite this: Catal. Sci. Technol., 2016,
6, 1265 valuable products
E. Pérez-Mayoral,*a V. Calvino-Casildaa and E. Soriano*b
Carbon materials such as activated carbons and graphitic materials and nanomaterials have been used for
Received 28th August 2015, decades in heterogeneous catalysis as catalyst supports. The physical and chemical properties of these ma-
Accepted 13th January 2016
terials, such as their tunable porosity and surface chemistry, allow the anchoring and dispersion of the ac-
tive phases, and make them suitable for application in many catalytic green processes. In this review, we
DOI: 10.1039/c5cy01437a
summarize relevant applications and limitations of metal-supported carbons and nanocarbons in the syn-
www.rsc.org/catalysis thesis of valuable products and the recent advances in this field.
1. Introduction organic solids such as silica, zeolite and mesoporous mate-

rials, among others. Therefore, the selection of the appropri-
Traditional heterogeneous catalysts often exhibit relatively ate support is a topic of main importance.
low activities because of the limited accessibility of the re- For a long time, carbon-based materials have been found
agents to the catalytically active sites. This drawback can be to be useful materials in catalysis as catalysts or even as sup-
overcome by supporting the active phases on other porous in- ports of catalysts.1 Among the advantages of these carbon-
based materials for catalytic applications are their i) high
a
Departamento de Química Inorgánica y Química Técnica, Universidad Nacional chemical stability in acid or basic media, ii) low corrosion ca-
de Educación a Distancia, UNED, Paseo Senda del Rey 9, E-28040 Madrid, Spain.
pability, iii) high thermal stability, iv) hydrophobic character,
E-mail: eperez@ccia.uned.es
b
Instituto de Química Orgánica General, CSIC, C/Juan de la Cierva 3, E-28006 v) easy recovery from the reaction mixture and, vi) from the
Madrid, Spain. E-mail: esoriano@iqog.csic.es economic point of view, their lower price. In fact, some
Elena Pérez Mayoral studied Vanesa Calvino-Casilda obtained

Chemical Sciences at the her Ph.D. degree at the UNED
Complutense University of Ma- (Madrid, Spain) in 2008 under
drid (UCM, Spain) where she the supervision of Prof. Rosa Mª
obtained her Ph.D. in 1999 Martín-Aranda and Prof.
concerning organic photo- Antonio J. López-Peinado. Later,
chemistry. After a post-doctoral she worked in the Catalytic
stay at the National Distance Spectroscopy Laboratory as a
Education University (UNED) postdoctoral researcher at the
and at the J. Heyrovsky Institute Institute of Catalysis and Petro-
of Physical Chemistry (the Acad- chemistry (CSIC, Madrid) under
emy of Sciences of the Czech Re- the supervision of Prof. Miguel
E. Pérez-Mayoral public, Prague), she became an V. Calvino-Casilda A. Bañares (2008–2013). Since
Assistant Professor at the UNED 2014, she has worked at the Fac-
in 2011. She has worked in different research fields, including me- ulty of Science (UNED, Madrid) as a postdoctoral researcher/
dicinal chemistry, on the synthesis of cyclin-dependent kinase in- teaching staff. Her research focuses on the intensification of
hibitors and on the design of lanthanide complexes as contrast heterogeneous catalytic processes for fine chemical synthesis and
agents for magnetic resonance imaging (MRI). Her current re- real-time Raman reaction monitoring.
search interests are focused on the design of new nanocatalysts in-
volved in the synthesis of biologically relevant heterocyclic systems
and related compounds.
This journal is © The Royal Society of Chemistry 2016 Catal. Sci. Technol., 2016, 6, 1265–1291 | 1265
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Minireview Catalysis Science & Technology
carbon materials stand out for their industrial applications

as adsorbents2 and especially in fine chemical production.3
Generally, the carbon materials with catalytic applications
have a graphitic structure, where the π-electron system of the
basal planes is responsible for the basicity of these mate-
rials.4 Furthermore, the concentration and nature of the or-
ganic functional groups, bearing different heteroatoms
(mainly O, N, H, Cl, S), over the surface of the carbon, con-
tribute to the changes in their acid–base character and redox

properties (Fig. 1), thus affecting their textural properties to a
greater or lesser extent, and playing a crucial role in their cat-
alytic behaviour.
The oxygenated groups are the most extensively investi-
gated functionalities due to the fact that the oxygen com-
bined with the carbon atoms forms a wide variety of organic
acid and base functionalities. It is well known that these
functionalities are easily formed during the synthesis or by
oxidant post-treatment of the corresponding carbon material
and, even, by exposure of the material to the atmosphere it-
self.5 While the carboxylic acids and anhydrides, lactones or
lactols, and phenols exhibit an acid character, the carbonyl
and ether groups are considered neutral functionalities.
Other organic oxygenated functionalities, such as quinone,
chromene and pyrone are proposed, although without con-
sensus, as basic oxygen-containing functionalities which
Fig. 1 Organic functional groups on carbon materials.
might be involved in surface redox processes.
In this sense, the quantum chemical calculations reported
by Fuente et al.6 concerning the pyrone-like model com-
pounds suggest that these organic functional groups are rele- the carbon-based materials most frequently used as the sup-
vant for carbon basicity. The calculated pKa values for these ports of the active phases, mainly due to their high surface
functionalities, in the range of 4–13, depend on the relative areas.7
position of the ketone and etheric rings. Carbon is, then, considered an old8 but also a new cata-
Many types of carbon materials have been used to prepare lytic material. In the past decades, the development of new
carbon-supported catalysts, such as carbon black, activated nanocarbons, also known as nano-structured carbon mate-
carbon (AC), glassy carbon, pyrolytic carbon and polymer- rials, including the modification and functionalization of the
derived carbon. Among them, the ACs and carbon black are different carbon allotrope structures with interesting applica-
tions, has undergone spectacular progress (Fig. 2).9
Nowadays, three different nanocarbon generations with
Elena Soriano obtained her Ph. catalytic applications are recognized: i) the 1st generation,
D. degree in 2003 at the UNED
(Madrid). She was a postdoc-
toral fellow of Gobierno de La
Rioja (2005–2006) and MEC
(Juan de la Cierva contract,
2006–2008) working at the IIB
“Alberto Sols” (UAM-CSIC). In
2008, she was granted a Ten-
ured Scientist position in the
Spanish Council for Scientific
Research (CSIC) at the Instituto
E. Soriano de Quimica Orgánica General
(Madrid), and in 2015 she has
been promoted to Senior Researcher Scientist. Her research inter-
ests focus on the application of computational tools to the study
of reaction mechanisms (mainly processes catalyzed by transition Fig. 2 Allotropes of carbon. Reprinted with permission from ref. 9.
metals and organocatalysis) and drug design. Copyright © 2007 Wiley-VCH.
1266 | Catal. Sci. Technol., 2016, 6, 1265–1291 This journal is © The Royal Society of Chemistry 2016
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characterized by low dimensionality and morphology-defined organic chemistry. Among them, the Heck C–C coupling reac-
properties, such as fullerene (zero dimension), CNTs (one di- tions are of growing interest in the fine chemical industries.
mension), graphene (two dimensions) and mesoporous car- In 1972, Heck et al.11 found that heterogeneous palladium
bons (three dimensions) and their derivatives; ii) the 2nd catalysts supported on AC (Pd/C) could perform the substitu-
generation, in which heteroatoms are introduced; and iii) the tion of vinyl derivatives with aryl halides, although with infe-
3rd generation, including the designing of hybrid and/or hi- rior yields to those obtained using homogeneous palladium
erarchical systems. catalysts. Later, it was demonstrated that there is a close cor-
Depending on the preparation and functionalization, nano- relation between the properties of the Pd/C catalysts and the
carbons can show a rich functional surface activity, with differ- reaction efficiency, and it depends mostly on the type of reac-
ent types of surface groups, showing themselves a rich catalytic tion.12 One of the most critical parameters for the Pd/C cata-
chemistry. Thus, the electronic structure is tailored by introduc- lysts is the palladium distribution. Thus, Pd/C catalysts are
ing heteroatoms, their physical properties are tuned by control- classified into “eggshell”, “thickshell” and “uniform”. In the
ling the pore structures, and their chemical properties are case of the “eggshell” catalysts, palladium is distributed
changed by specific surface functional groups. In other words, a closely to the surface within 50–150 nm depths, whereas in
level of control in the characteristics of the nanocarbon is intro- the “thickshell” catalysts, palladium is distributed to depths
duced during the synthesis or by post‐synthesis treatments. In of 200–500 nm from the surface. In contrast, palladium is
addition, a further level of control in the properties of nano- dispersed homogeneously in the “uniform” catalyst. Arai
carbons can be reached by designing hybrid and/or hierarchical et al.13 elucidated the mechanism of the palladium supported
systems. These materials are nano‐architectured, e.g. the reactiv- on AC catalyzed Heck coupling reaction. In the reaction of
ity properties depend critically on the nano‐architecture, not iodobenzene with methyl acrylate in the presence of Pd/C, tri-
only in terms of mass transfer, the classical motivation to realize ethylamine and sodium carbonate, at 160 °C, triethylamine
hierarchical structured catalysts. seemed to reduce PdĲII) to Pd(0), while the role of sodium car-
The synthesis and application of carbon-supported catalysts bonate was to neutralize the acid formed during the reaction.
have been the subject of several reviews.1a,10 However, the goal On the other hand, the use of trimethylamine, besides so-
of this paper consists of an update addressed to review the ap- dium carbonate, led to a high rate acceleration and a major
plications of metal-supported carbons and nanocarbons, partic- recovery of palladium. Moreover, the reaction seemed to take
ularly in the synthesis of valuable products. This contribution place when the colloidal palladium, which is obtained by par-
pays special attention to the use of ACs as their unique proper- tial aggregation of the dissolved palladium, was redissolved
ties make them one of the most preferred supports. catalyzing again the reaction.
Köhler et al.14 found that oxidic uniform Pd/C catalysts
2. Activated carbons with a high water content (55%) were active catalysts in the
Heck coupling of bromobenzene with styrene, affording
ACs are the most studied carbon-based material as supports trans-stilbene in high yield and selectivity (Scheme 1). It
for noble metals. The high dispersion and stability of the me- seemed that the water content in the Pd/C catalysts acceler-
tallic phases on ACs are possible mainly due to their large ated the reaction, inhibiting the precipitation of the inor-
surface areas.5a In some cases, the presence of functionalities ganic species on the surface of the metal. In addition, the
over their surface is especially relevant for anchoring the me- palladium dissolved in the solution appeared to catalyse the
tallic phases even as coordination complexes. Both the tex- reaction, increasing also its average size with the reaction
ture and surface chemistry of ACs influence the catalytic per- time. Thus, the Pd/C catalysts changed their morphology
formance of AC supported catalysts. ACs are used from uniform to eggshell, with palladium deposited mostly
commercially in many catalytic formulations, particularly for on the surface of the support. Therefore, Pd leaching of
hydrogenation catalysts, for the excellent properties of disper- heterogeneous catalysts was required for high activity and se-
sion of metal particles (particularly based on noble metals) lectivity in the Heck reactions.15
and the absence or (limited) presence of sites, which may ca- Later, Fan et al.16 carried out the continuous multi-step
talyse side reactions. In addition, they are less expensive com- synthesis of 1,2-diphenylethane in a structured compact
pared to alumina and silica supports and the active phase multichannel reactor. The reaction involved a Heck C–C cou-
can be recovered by eliminating the support through burning pling reaction followed by the reduction (alkene hydrogena-
away the carbon. In the subsequent sections we review the tion) of the intermediate obtained (Scheme 2). Microspheri-
types of metal-supported ACs involved in the catalytic pro- cal AC-supported Pd catalysts catalysed both steps. The flow
cesses of fine chemicals.
2.1 Metal supported ACs

Metal supported ACs have been used for a variety of chemical
reactions, mainly C–C coupling reactions, hydrogenations, ox-
idations or carbonylations. The C–C bond forming reactions Scheme 1 Heck coupling reaction of bromobenzene with styrene
are fundamental and versatile transformations in synthetic over a Pd/C catalyst.
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process in the compact reactor was more efficient than in the

discontinuous reactor (batch). Thus, the reaction time was re-
duced significantly from hours to minutes, additional ligands
were also not used, and the reaction was carried out under
milder reaction conditions (lower values of pressure and tem-
perature). The Pd leached in the Heck C–C coupling step was
efficiently recovered in the following reduction step. In this
Scheme 3 Synthesis of a biphenylacetic acid derivative over a Pd/C
manner, a reverse flow operation could normally retain the catalyst.
catalytic activity of the system demonstrating that a compact

reactor was capable of carrying out the multi-step synthesis
in only one stream.
The importance of developing carbon catalysts for use in spherical polyĲN-vinyl-2-pyrrolidone) palladium nanoparticles
Suzuki cross-coupling reactions with aryl chlorides has in the Suzuki reaction between phenylboronic acid and iodo-
aroused great interest. Buchecker et al.17 carried out the benzene to obtain biphenyls. The carbon-supported colloidal
Suzuki–Miyaura coupling of aryl bromide with aryl boronic Pd nanoparticles showed higher activity during the first cycle
acid, in the absence of phosphine ligands, using Pd/C hetero- of the reaction than the carbon-supported spherical Pd nano-
geneous catalysts. The procedure was only valid to aryl bro- particles. However, after the second cycle, the carbon-
mides and iodides but not for aryl chlorides because a signif- supported Pd nanoparticles showed a recycling potential that
icant degree of hydrodechlorination was observed. The is double that of the colloidal Pd nanoparticles. Moreover,
authors performed some additional experiments with the Pd/ the catalytic activity of the carbon-supported colloidal Pd
C catalysts and concluded that under the reaction conditions nanoparticles decreases during the following second to fifth
used, the coupling reactions occurred by heterogeneous catal- cycles of the Suzuki reaction while the catalytic activity of the
ysis. In the literature, Pd(0) was always suggested to be active carbon-supported Pd nanoparticles remains almost constant.
as a complexed homogeneous species in this type of reac- It seemed that the particle size played a significant role. The
tions, however in this case the authors demonstrated, for the carbon support protected the Pd nanoparticles during the re-
first time, that Pd(0) acted in a heterogeneous form. Then, action preventing aggregation and precipitation in contradis-
Gala et al.18 showed, for the first time, that the carboxylic tinction to the colloidal Pd nanoparticles. After these re-
acid group is compatible with the Suzuki reaction. They ac- search studies, Köhler et al.21 exposed that hydrophobic
complished the synthesis of a biphenylacetic acid derivative surfaces, such as those shown by Pd/C, play an important
through coupling of an arylboronic acid (derived from a Gri- role in the Suzuki coupling reactions in water showing high
gnard reagent) with bromophenylacetic acid over the Pd/C activity (Scheme 4). However, those catalysts with hydrophilic
catalysts. The reaction procedure, without phosphine ligands surfaces, like palladium on metal oxides, showed low activity
and degassed solvents, afforded the coupling product in a for the Suzuki coupling reactions in water. In this case, these
good yield (Scheme 3). The process was also scaled up to a catalysts could improve their catalytic activity by tuning the
multikilogram preparation of 4′-fluorobiphenylacetic acid. surface polarity of the metal oxide supports or using stronger
Sun et al.19 reported the Suzuki cross-coupling reaction alkaline conditions (adding an excess of base). The hydropho-
with aryl chlorides over Pd/C catalysts without added ligands. bic surface of the Pd/C catalysts with better catalyst disper-
It seems that both the tri-tert-butylphosphine and sion in the phase containing organic substrates might cause
triphenylphosphine ligands poisoned the reaction. They enrichment of the substrate at the catalytic surface. The
suggested that a synergistic anchimeric and electronic effect supported Pd in contact with the substrate was responsible
that takes place between the Pd surface and the aryl chloride for the formation of the active species that resulted in higher
could explain the C–Cl bond activation. The selection of the conversions. It seemed that the reaction occurred near the
suitable reaction medium was also crucial for this cross- catalyst surface, within a droplet or layer of the catalyst
coupling reaction. Then, El-Sayed et al.20 compared the cata- substrate.
lytic activity of carbon-supported spherical polyĲN-vinyl-2- The exclusive homogeneous or heterogeneous catalysis of
pyrrolidone) palladium (PVP-Pd) nanoparticles and colloidal the Suzuki reaction seems to be inconsistent as anticipated;
some authors suggest then the possibility of the “soluble” Pd
Scheme 4 Suzuki coupling reaction of 4′-chloroacetophenone cata-

Scheme 2 Synthesis of 1,2-diphenylethane over a Pd/C catalyst. lyzed by Pd/C or Pd/Al2O3 in water.
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nanoparticle formation after Pd leaching from the surface of affected by the support, the platinum loading and the condi-
the supported catalysts. To this end, Kçhler et al.22 reported a tions used during the deposition, keeping the same metal
highly active and robust heterogeneous Pd-based catalyst (Pd/ precursor. The Pt/C catalysts were active in the isopropyl alco-
C, Pd/metal oxides and Pd/zeolite) for the Suzuki reactions hol oxidation probe reaction showing an almost total alcohol
leading to the corresponding biaryls with total selectivity conversion and a TOF of 80 000 h−1.
without exception, in quantitative yields and with short reac- Halttunen et al.27 explored the stability of Rh and Ru cata-
tion times. The catalysts were reusable several times by the lysts supported on AC in the hydrocarbonylation of methanol
addition of iodine as an oxidizing agent. The authors con- in the liquid phase. The metal dispersion was related to the
cluded that the Pd concentration in solution during the reac- stability of the Rh-supported catalysts, with the stability
tion correlates clearly with the progress of the reaction (con- worse when the dispersion was higher. The catalytic activity
version) indicating that the dissolved molecular Pd is the showed by the Rh supported on AC catalysts was related to
catalytically active species; after the end of the reaction, the the amount of metal leached from the support. They con-
dissolved Pd is deposited onto the support. cluded that these heterogeneous catalysts were not appropri-
Hermans et al.23 prepared palladium carbon (Pd/C) ate for the methanol hydrocarbonylation in the liquid phase
supported catalysts using precursors of grafting carboxylate but they could be in the gaseous phase. Then, Wettstein
on functionalized carbon. The carbon supports were func- et al.28 prepared RuSn supported on AC as catalysts varying
tionalized by treatment with HNO3 and H2O2, and the corre- the tin content for the levulinic acid hydrogenation to
sponding oxygenated functionalities formed were used as an- γ-valerolactone. The addition of Sn to the Ru/C catalysts sig-
chors for the Pd precursors, Pd carboxylate complexes nificantly influenced the catalytic properties, improving the
(PdĲO2CR)2ĲN-ligand)x), by covalent bonding. The Pd/C cata- selectivity and stability in the studied reaction. The catalyst
lysts were used in the 2-methyl-2-nitropropane hydrogenation containing only Ru was the most active catalyst but
to obtain t-butylamine. Apparently, there was a correlation be- underwent deactivation with the time on stream. However,
tween the catalytic activity and both the initial carbon acidity the catalyst containing the same amounts of Ru and Sn
and Pd dispersion, in the case of the HNO3-modified sam- showed a lower activity but improved stability and selectivity
ples. This was not the case for the H2O2-modified samples, with the time on stream. Increasing the Sn content triggered
probably due to the presence of different types of oxygenated the formation of an additional phase (β-Sn) that was not ac-
surface groups. They served as anchors for the Pd precursors tive under the reaction conditions. From all the RuSn
playing an important role during the catalytic process. Then, supported on AC catalysts prepared, the RuSn4/C catalyst was
Okhlopkova24 studied the influence of the acidity of the solu- the most active and stable catalyst to produce γ-valerolactone.
tion on the dispersion of platinum supported on an AC cata- Recently, Zhao et al.29 carried out the chemoselective reduc-
lyst and its activity in the hydrogenation of cyclohexene. An tion of different substituted nitroarenes to obtain different
acidic solution indeed influenced the platinum dispersion, functionalized arylamines using supported Co-promoted Mo
decreasing the activity of Pt/C in the cyclohexene hydrogena- carbide catalysts on modified AC (Co–Mo2C/AC) (Scheme 5).
tion when the dispersion is increased. This fact was due to The addition of a small amount of a transition metal such as
the localization of the metal species in the narrow pores of Co seemed to promote considerably the formation of the mo-
the support blocking the access of reagents. This effect lybdenum carbide crystal phase. This resulted in an improve-
seemed to be larger on those supports containing smaller ment in the catalytic activity of the supported molybdenum
pores and a higher concentration of the oxygen functional carbide catalyst due to a synergistic effect, affording a total
groups. Later, Davis et al.25 reported supported bimetallic Pt– conversion and selectivity in all the cases. The Co–Mo2C/AC
Re nanoparticles on Norit AC for the glycerol hydrogenolysis catalyst could be considered for industrial applications re-
reaction. The bimetallic Pt–Re clusters on AC were more ac- lated to the production of functionalized arylamines. Lately,
tive than either monometallic Pt or Re. Catalysts containing Gallegos-Suárez et al.30 supported Ru on different carbon ma-
Re could only be reduced under hydrogen when coexisting terials (AC, graphite and multi-walled carbon nanotubes) for
with Pt, apparently by spillover dissociated hydrogen atoms use as catalysts (Ru/AC, Ru/HSAG and Ru/CNT) in the hydro-
from Pt to Re. The Pt–Re/C catalyst achieved a better catalytic genolysis of glycerol in the liquid phase. The CO microcalo-
performance when sintered at high temperatures, enhancing rimetry results showed that the graphite and carbon nano-
the atomic mixing of Pt and Re and not decreasing consider- tube supports possess electron donor properties capable of
ably the metal dispersion. More recently, Kaprieloba et al.26
prepared Pt/C catalysts by reductive deposition in the aque-
ous phase. The AC support worked as an effective nucleating
agent and ensured the formation of small Pt particles
avoiding the formation of aggregated Pt particles. This fact
was probably due to the oxide nucleus formation on the AC
surface. The high deposition rate provides Pt nanoparticles Scheme 5 Chemoselective reduction of various substituted
in the narrow pores and outside of the micropores (eggshell nitroarenes to the corresponding functionalized arylamines over the
Pt distribution). Thus, the catalytic properties could be developed supported metal carbide catalysts on AC.
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promoting the formation of an electron-rich metal species and pharmaceuticals, among other applications.33 This pro-
(Ruδ−). Thus, Ru supported on graphite and carbon nanotube cess often requires the use of stoichiometric amounts of
catalysts promote 1,2-propanediol formation from glycerol, highly contaminant inorganic oxidants such as chromiumĲVI)
and improve the consecutive C–C cleavage forming undesired salts. Therefore, the development of new methodologies with
products, such as methane (Ru/CNT > RuHSAG). On the other reduced environmental impact using clean oxidants, H2O2, or
hand, Ru supported on AC showed ethylene glycol as the main even operating under aerobic conditions is a challenge of
product in the conversion of glycerol on the metal sites. prime importance.
Kim et al.31 studied palladium and copper supported on In this sense, manganese oxide and vanadium oxide-
supported AC catalysts have been reported by Chen et al.34
AC catalysts for the oxidative carbonylation of phenol and

bisphenol-A to obtain diphenyl carbonate or polycarbonate for the aerobic and selective oxidation of benzyl alcohol to
oligomers used as intermediates in the phosgene-free poly- benzaldehyde. An enhancement of the catalytic activity (from
carbonate synthesis. Metallic Pd with some fraction of its sur- 31 to 67% when using Mn/C-0.5 M HNO3 and from 46 to
face oxidized, and cuprous oxide were the initial states of Pd 93% for V/C-O2 for 3 h) was observed when the metal oxides
and Cu when they were supported on AC. However, the me- were supported using the previously oxidized AC support. It
tallic character of Pd was enhanced during the oxidative car- is probably due to the presence of the specific variety and the
bonylation and the Pd–Pd coordination number increased to increased density of the oxygen-containing complexes on the
almost twice. In the case of the copper supported on AC cata- AC support surfaces. The ACs under study showed similar
lyst, cuprous oxide (initial state) was converted into a rare lin- particle dispersion and the metallic centers maintained the
ear cuprous dibromide complex that was stabilized by a tetra- oxidation state and coordination environment before and af-
butylammonium cation. The cuprous complex seemed to be ter oxidant pretreating of the AC support.
the active key catalytic component to obtain the desired aro- Zhu et al.35 reported a cheap, effective and reusable
matic carbonates. On the other hand, the role of the carbon- Co3O4/AC catalyst, working in the absence of any promoter,
supported metallic Pd catalyst in the oxidative carbonylation for benzyl alcohol oxidation, in the presence of molecular ox-
of phenols was the oxidative regeneration of hydroquinone to ygen under mild conditions. Among the metal oxides investi-
benzoquinone with the production of water as the by-prod- gated by the authors, Co and Ni oxide supported ACs were
uct. This research group also studied the coupled oxidative the most promising catalysts for the aerobic oxidation of ben-
carbonylation of bisphenol-A and phenol using Pd/C catalysts zyl alcohol, whereas other metal oxides such as the Mn, Fe,
and different metal complexes of Ce, Co, Mn and Cu as inor- and Cu ones exhibited lower conversion and selectivity.
ganic co-catalysts (Scheme 6).32 The heterogeneous catalytic Co3O4/ACs were prepared by a wet impregnation method and
system formed by Pd supported on AC and Cu2O as a co- subsequently first dried in an air oven at 110 °C overnight
catalyst showed improved catalytic properties with better ac- and then treated in N2 or Ar at 350 °C. Quantitative conver-
tivity and selectivity results than the Pd homogeneous sys- sion of the alcohol was obtained when using the samples
tem. The active phase of the Pd/AC–Cu2O–Bu4NBr–BQ cata- treated under an Ar atmosphere. It is noteworthy that these
lytic system was established by the metallic Pd particles with catalysts can be reused without any significant activity loss.
the catalytic performance independent of the Pd initial state The authors proposed a plausible reaction mechanism for
in Pd/AC as was evidenced by the Pd K-edge EXAFS studies. this transformation consisting of two fundamental steps: i)
the molecular oxygen activation occurring by adsorption on
the defects on the carbon support, and ii) the alcohol dehy-
2.2 Metal oxide supported ACs drogenation taking place over Co3O4. The high catalytic activ-
Metal oxide supported AC catalysts have been successfully ity observed for the cobalt-supported ACs was comparable to
used for a great variety of chemical reactions, such as oxida- the other noble metal-supported AC catalysts, such as Au/AC.
tions, reductions, transesterifications, or alkylations, among The epoxidation of olefins plays an important role in the
others. Selective oxidation of alcohols into the corresponding industrial production of fine chemicals. Particularly, ethylene
aldehydes/ketones is a transformation extremely useful in or- oxide and its derivatives are extensively used for multiple ap-
ganic synthesis (Scheme 7). The carbonyl components are in- plications in the production of electronics, pharmaceuticals,
volved in the production of plastic, dyestuff, perfume, flavor pesticides, detergents, among others.36 In this regard, a well-
Scheme 6 Synthesis of mono phenylcarbonate-ended oligomers (denoted as MpC(n)) over palladium catalysts.
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produced from ethylbenzene (EB) by dehydrogenation using

α-Fe2O3–K2CO3. Several researchers have reported the effect
Scheme 7 Oxidation of alcohols into the corresponding carbonyl of using different porous catalytic systems in the presence or
compounds. absence of CO2 as an alternative diluent. However, the tradi-
tional catalyst above mentioned used for ST production did
not exhibit significant catalytic activity when using CO2 (yield
dispersed tantalum oxide on an ordered mesoporous carbon to ST 1.9%). In this respect, Sugino et al.40 reported the dehy-
(CMK-3 or CMK-1) catalyst tested in the epoxidation of cyclo- drogenation of EB catalyzed by a different series of carbon-
octene, in the presence of aqueous H2O2, has been reported supported iron catalysts. These catalysts were prepared by im-
by Lin et al. (Scheme 8).37 pregnating a carbon support with aqueous solutions of iron
CMK-3 and CMK-1, as carbon replicas of the mesoporous nitrate. In the case of the carbon-supported iron catalysts co-
silicas SBA-15 and MCM-48, respectively, exhibited higher cat- loaded with an alkali metal and an alkaline earth metal, they
alytic performance, excellent selectivity and recyclability than were prepared by either successive impregnation of a carbon
tantalum oxide supported on AC and also over mesoporous support with solutions of an iron nitrate and alkali metal or
silica SBA-15. While all of the investigated catalysts supported alkaline earth metal nitrates, or by co-impregnation using so-
on carbon showed high epoxide selectivities (around 85%), lutions containing both salts. The investigated carbon-
the use of the tantalum oxide supported on SBA-15 catalyst supported iron catalysts afforded a high ST yield (up to 50%)
afforded the corresponding epoxide with a lower selectivity in the presence of excess CO2. The increased loading of lith-
(65%). This catalytic behavior could be attributed to the use ium nitrate (0.1 to 0.3 mol to 1 mol of the iron catalyst) par-
of carbon supporting metal oxides that provide an adequate ticularly resulted in a significant increase in the catalytic ac-
hydrophobic environment for the catalytic sites, thus facilitat- tivity. In this case, under pretreatment of the catalyst with
ing the adsorption of olefins for selective epoxidation. CO2, at 973 K, iron and lithium on the carbon surface were
Metal oxide supported ACs have been also reported for converted into magnetite and lithium ferrite. Then, it seems
interesting reduction reactions, such as the synthesis of ani- that the lithium ferrite phase was found to be the active
lines from nitro arenes or dehydrogenation of alkyl benzenes. phase in the reaction of EB to ST. The authors proposed the
It is important to note that anilines are key intermediates for following redox catalytic cycle: i) the lattice oxygen of iron ox-
the synthesis of pharmaceuticals, herbicides, polymers, and ide in lithium ferrite abstracts the hydrogen from EB to give
other fine chemicals. Fluoroanilines (FA) are particularly im- ST and ii) CO2 oxidizes the oxygen defects in the iron oxide
portant building blocks involved in the synthesis of a great phase in lithium ferrite.
variety of biochemical products.38 The industrial production In a similar way, Saito et al.41 described the role of lattice
of anilines from nitroaromatics often is carried out in the oxygen in V, Cr, and Fe oxide-loaded catalysts in the dehydro-
presence of Pd/C catalysts, which exhibit a high intrinsic ac- genation of EB applying a transient response technique, an
tivity but also low selectivity to the desired product. efficient method for analyzing the performance in an un-
Zhao et al.39 synthesized and characterized a novel highly steady state catalytic reaction. As in the other cases, the cata-
selective and active carbon-supported Pd/SnO2 catalyst for lysts were prepared by impregnation of the support with an
the hydrogenation reaction of 2,4-difluoronitrobenzene aqueous solution of the corresponding metallic salts and sub-
(DFNB) to the corresponding 2,4-difluoroaniline (DFAN) in sequent calcination at different temperatures depending on
the presence of ethanol. The Pd/SnO2/C catalysts were pre- the used support. The best catalytic results were found for
pared by first deposition of the SnO2 onto the carbon sup- the dehydrogenation process catalyzed by the V, Cr, and Fe
port, followed by the deposition of Pd. The notable synergis- oxide/AC catalysts. In order to study the promoting effect of
tic effect of the Pd and SnO2 nanoparticles and significant CO2, the reaction was carried out using a fix bed flow type
performance and selectivity enhancements (Table 1) were quartz reactor operating at atmospheric pressure and the de-
reported. These results are probably because of the coordina- hydrogenation of EB was carried out under Ar and CO2 atmo-
tion action between the NH2 groups and the Sn2+ or Sn4+ spe- spheres. While in the presence of Ar, the lattice oxygen of the
cies at the surface of SnO2, produced under a H2 reductive at-
mosphere, forming Pd–Snn+ ion pairs.
One of the other most important basic chemicals in the Table 1 Hydrogenation of DFNB promoted by Pd catalystsa
petrochemical industry is styrene (ST). It is industrially
Catalyst Conversion (%) Selectivityb (%) Reaction ratec
Pd/C 100 96.47 1.99
Pd/SnO2 100 99.96 0.84
Pd/SnO2/C 100 100 3.72
a
Reaction conditions: 0.1 g of catalyst, 20.0 g of DFNB, 15 mL of
EtOH, PH2 = 1.0 MPa, T = 353 K, stirring rate = 1000 rpm. b Only
aminodiphenylaniline and nitrodiphenylamine were detected among
Scheme 8 Epoxidation of cyclooctene, in the presence of aqueous the other by-products. c Expressed in mol of substrates per mol of
H2O2, catalyzed by supported tantalum oxide. Pd.
View Article Online
vanadium and iron oxides was transferred to EB at the begin- precursors, respectively. The combined materials are rich in
ning of the reaction; under CO2, the transferred lattice oxy- MgO and revealed a bimodal, microporous–mesoporous char-
gen was supplied partially from CO2 to keep the vanadium or acter. These materials were investigated in the Friedländer
iron oxides as higher valence state oxides. The plausible condensation46 of 2-amino-5-chloro-benzaldehyde and
mechanism for the dehydrogenation of EB over V, and Fe ox- acetylacetone (R1 = R2 = Me), under solvent-free and mild
ide/AC, under CO2, is summarized in Scheme 9. In contrast, conditions, affording the corresponding quinoline in good to
when using the Cr2O3-loaded catalysts, no significant oxygen excellent yields (up to 76%) with total regioselectivity
transfer from the lattice oxygen of Cr2O3 to EB was observed (Scheme 10). The results reported demonstrated that MgO is
and, hence, no promoting effect of CO2 was observed. the main catalytically active species. The activity of the cata-
Biodiesel fuel prepared from renewable sources is consid- lysts apparently did not correspond to the MgO loading, but
ered as an alternative to diesel fuel. It is produced by the depended on the available catalytically active surface of the
transesterification reaction of triglycerides from oils and fats MgO crystals on the hybrid materials.
with low-molecular-weight alcohols; CaO exhibits high activ- The scope of the methodology was demonstrated by
ity for this transformation. However, the main disadvantage reacting different 2-aminoaryl aldehydes and also different
of using CaO as a catalyst in the biodiesel production is the 1,3-dicarbonyl compounds leading to the corresponding bio-
formation of the CaO–glycerin complex42 acting then as a logically active heterocyclic compounds, such as
homogeneous catalyst. To overcome this drawback, Zu naphthyridines and acridones.
et al.43 selected different porous carbon materials, such as On the basis of the DFT calculations, a reaction mecha-
carbon molecular sieves, AC, and the nanoporous carbons nism was postulated.45 This analysis suggested a dual activa-
NC-2 and CMK-3, as supports in the synthesis of active and tion by the catalyst, as both carbonyl compounds are acti-
stable CaO-based catalysts for the transesterification of vated for the condensation (Scheme 11).
triacetin with methanol. Among the investigated supports, Carbon is known as a very efficient absorber of microwave
NC-2 with mesoporous and/or microporous characteristics, (MW) energy as it effectively transforms the energy into heat.
showed very high activity, stability, and recyclability. In this context, the use of alkaline carbons such as alkaline
In the same way, carbon-supported MgO nanocomposites metal oxides supported over Norit carbon has been widely ex-
based on the NC-2 carbon material were investigated in the plored in our research group by combining alternative energy
synthesis of ethyl methyl carbonate (EMC) prepared by the sources (MW and ultrasound). Thus, basic carbons are able
transesterification reaction of dimethyl carbonate (DMC) with to catalyze selectively the N-alkylation of imidazole with
diethyl carbonate (DEC).44 It was observed that MgO/NC-2 propargyl bromide, under MW irradiation.47 The activity of
with different MgO loadings (1.6 to 20 wt%) exhibited a re- the catalysts increased with the irradiation power, yielding
markably higher transesterification activity than the other N-propargyl imidazole in the highest conversion values when
carbon-supported MgO catalysts. The presence of a high con- using Cs+-Norit carbon (an almost quantitative yield, with
centration of oxygen functionalities over the surface of the 100% selectivity, in 3 min of reaction time). In addition, the
NC-2 support probably favored the high dispersion of the selective N-alkylation of imidazole and 2-methylimidazole
MgO particles. In this case, MgO/NC-2 showed high stability with long-chain and medium-chain alkyl bromides, yielding
against leaching of the active species under the test reaction imidazole derivatives exhibiting valuable pharmacological
conditions, indicating the truly heterogeneous nature of this properties, such as antiparasitic, antifungal, and antimicro-
catalyst. bial, was also reported (Scheme 12).48 The N-alkylation of
Some members of our research group reported MgO- benzimidazole was also effectively performed, under MW ac-
supporting carbon materials, PET/MAG, for the synthesis of tivation, over basic carbon catalysts selectively yielding the
relevant nitrogen heterocyclic compounds, as a highly effi- corresponding alkylated heterocyclic compound in a high
cient sustainable alternative to the amino-grafted and bifunc- yield in very short reaction times (75% in only 5 min of reac-
tional mesoporous silicas.45 These hybrid basic materials, tion time).49 Furthermore, the imidazole alkylation reaction,
containing different MgO loadings, were synthesized by ther- under ultrasound activation, was also investigated by some of
mal calcination of homogeneous mixtures of polyĲethylene
terephthalate) and magnesite, both as carbon and MgO
Scheme 9 Proposed reaction courses for the dehydrogenation of EB Scheme 10 Friedländer condensation of 2-aminobenzaldehydes and
to ST under CO2. 1,3-dicarbonyl compounds.
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Scheme 13 Michael addition of imidazole and ethyl acrylate for the

synthesis of N-substituted imidazole catalysed by basic carbon.
2.3 Immobilized coordination complex over ACs

Immobilized coordination complex over a solid support is a

novel hybrid catalytic system able to merge the advantages of
heterogeneous and homogeneous catalyses. This material has
been used mainly in catalytic hydrogenation and oxidation
reactions. The immobilization of the coordination complex
over an AC support has received special attention due to the
possibility of fine-tuning its textural properties and surface
chemistry rich in oxygen functional groups. Palladium com-
Scheme 11 Postulated reaction mechanism on the basis of DFT
calculations. plexes containing aromatic ligands were the first coordina-
tion complexes immobilized over AC supports, whose cata-
lytic activity was highly dependent on the location of the
palladium center.54 This study shows the importance of the
us.50 Thus, for the reaction between imidazole and metal complex position on the accessibility of the reactants
1-bromobutane promoted by alkaline carbons, an enhance- to the active centers. Later, Bischoff et al.55 prepared AC
ment effect in the yield of the alkylated imidazole was supported rhodium–phosphonate–phosphane catalysts for
observed. use in methanol carbonylation. They found that AC was a
Another method, the real-time Raman monitoring of imid- suitable support for hemilabile rhodium complexes but nor-
azole alkylation and the Michael addition reaction between im- mal diffusion of reactants, at higher pressures, begins to
idazole and ethyl acrylate, promoted by these basic carbon and limit the intrinsic high activity of the supported complexes.
other acidic catalysts, has been also reported (Scheme 13).51 AC-heterogenized [PdCl2ĲNH2ĲCH2)12CH3)2] catalysts were se-
This non-invasive methodology provides molecular informa- lective catalysts for the hydrogenation of 1-heptyne, where
tion on the reaction mechanism and possible species as in- the support porosity played an important effect.56 The posi-
termediates of the reaction. tion of the complex in the narrow pores induced shape selec-
Following the alkylation reaction of heterocyclic com- tivity due to the slit-shaped pores whereas ACs with a wider
pounds, Calvino-Casilda et al.52 reported for the first time an pore size distribution showed a negative effect in selectivity.
efficient and eco-friendly alternative for the preparation of The study was extended to other metal complexes with simi-
N-substituted-γ-lactams promoted by alkali-loaded catalysts, lar long-chain amine ligands. The authors proved that the an-
Na-Norit, Cs-Norit and the bimetallic NaCs-Norit, under chored rhodium complex [RhClĲNH2ĲCH2)12CH3)3] supported
solvent-free conditions and MW irradiation. The carbon–ni- on AC is an active and selective catalyst in the semi-
trogen coupling reaction takes place between 2-pyrrolidinone hydrogenation of 1-heptyne.57 The coordination compound
and 1-heptanal selectively affording the N-1-heptenyl-2- was stable under the reaction conditions and was firmly at-
pyrrolidinone. A notable enhancing effect in the yield under tached to the AC support, constituting the active species of
MW irradiation was observed in comparison with the conven- the catalyst.
tional thermal activation methods (~70% yield in only 5 min Lemus-Yegres et al.58 prepared the diamine Rh complex
to ~50% after 1 h of reaction time) (Scheme 14). [RhĲCOD)ĲNH2ĲCH2)2NHĲCH2)3SiĲOCH3)3)]+BF4− supported on
These carbon catalysts were also used in the synthesis of AC catalysts for the hydrogenation of cyclohexene and carv-
chalcones, relevant intermediates in the synthesis of many one. For the first time, this research group exploited the phe-
pharmaceuticals, by Claisen–Schmidt condensation under ul- nolic surface groups of carbon materials for the immobiliza-
trasound irradiation (up to 50% yield) (Scheme 15).53 tion of metal complexes through the creation of siloxane
bonds (covalent bond) (Scheme 16). The active species were
Scheme 12 N-Alkylation of imidazoles with long-chain and medium- Scheme 14 N-substitution of 2-pyrrolidinone with 1-heptanal under
chain alkyl halides. MW activation over basic carbon catalysts.
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Scheme 15 Claisen–Schmidt condensation of substituted

benzaldehydes and acetophenone.
located inside the support porosity, where a minimum diam-

eter of pores was required for the confinement of the metal
Scheme 17 Catalyst formed by a rhodium complex anchored on
complex. After this study, further research was extended
activated carbon.
using ACs oxidized in various ways (HNO3, (NH4)2S2O8, and
synthetic air) in order to obtain different surface chemis-
tries.59 The results showed that the catalysts with large epoxide chemoselectivities.62 These authors also immobilized
amounts of oxygen groups hindered the location of the com- a Schiff base nickel complex functionalized with hydroxyl
plex inside the porosity of the support, thus displaying a low groups, N,N′-ethylene-bis-(4-hydroxysalicyliminate)nickelĲII),
catalytic activity. Then, this research group immobilized an onto an AC using cyanuric chloride as the linking agent.63
Rh complex derived from the Wilkinson's catalyst on AC Then, they anchored chiral manganeseĲIII) salen complexes
using an ester type covalent bond and a linear organic on modified AC supports by direct axial coordination of the
molecule (6-amino-1-hexanol) (Scheme 17).60 This molecule metal center onto the phenolate groups and tested them in
acts as a linker and positions the complex away from the sup- the epoxidation of ST.64 The modification of the AC was car-
port surface to simulate its environment in the homogeneous ried out by a reaction between sodium hydroxide and the sur-
phase. This catalyst was tested in the hydrogenation of cyclo- face phenol groups to obtain phenolate groups (CoxONa).
hexene resulting in a similar activity to the homogeneous They also studied the influence of the textural properties of
Wilkinson's catalyst. four ACs on the immobilization process and on the catalytic
The catalyst CpTiCl2ĲOC6H4Cl-p) was supported on three performance of the MnĲIII) catalysts.65 Their results suggested
AC supports obtained from different precursors and that the total MnĲIII) loadings increased with the pore size, as
subjected to ammoxidation in order to investigate the effect well as their distribution inside the carbon porous matrix.
of the presence of nitrogen species.61 These catalysts were Moura et al.66 anchored iridium clusters over AC to use as
tested in the polymerization of ST showing that those cata- heterogeneous catalysts in the selective hydrogenation of 1,5-
lysts modified by nitrogen species were less catalytically effec- cyclooctadiene. The formation of the fully hydrogenated prod-
tive because the active centers were present only on the sup- uct cyclooctane was observed when Ir metal supported on AC
port surface and not in the pores. was used as a catalyst. However, when Ir3 clusters were
ManganeseĲIII) salen complexes have been demonstrated immobilized on ACs, these catalysts showed a special catalytic
to be excellent catalysts in the epoxidation of behaviour producing high activity and selectivity for the mono-
unfunctionalized olefins, displaying high activity and hydrogenated product cyclooctene, and the isomerisation
enantioselectivity. Moreover, the hydroxyl groups, mainly the products 1,3-cyclooctadiene and 1,4-cyclooctadiene.
phenol type, present on the carbon surface or created by oxi- The current interest in transition metal complexes bearing
dation treatment, have been used to anchor the metal com- tripodal capping C-scorpionate ligands, HC(pz)3ĲTpm), and
plexes. A MnĲIII) Schiff base complex functionalized with hy- their derivatives, is due to their diverse applications, such as
droxyl groups on the aldehyde moieties [MnĲ4- in oxidation processes. Homogeneous and heterogenized
HOsalhd)CH3COO] onto an AC showed that the oxidation of AuĲIII) C-scorpionate complexes supported on carbonaceous
the support enhanced the catalyst adsorption whereas the materials (AC, carbon xerogel and carbon nanotubes) were
acidity of the carbon surface had a negative effect on the ST used as catalysts for the single-pot peroxidative cyclohexane
oxidation to cyclohexanol and cyclohexanone under mild
conditions (H2O2 as an oxidant), at room temperature
(Scheme 18).67 The previous oxidation of the carbonaceous
supports with HNO3 or their oxidation with HNO3 and subse-
quent treatment with NaOH led to the best heterogenization
performance.
Recently, Silva and Botelho68 immobilized FeĲII) and FeĲIII)
acetylacetonate onto amine functionalized ACs. The Fe com-
plexes were anchored onto AC supports functionalized with
Scheme 16 Metal complex anchored on carbon supports through the (3-aminopropyl)triethoxysilane (APTES), through Schiff con-
siloxane bonds. densation of the carbonyl groups of the acetylacetonate
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ligands and the APTES amine. The immobilized iron salts loading.74 In addition, the deactivation of the catalyst oc-
were active heterogeneous catalysts in the oxidation of cyclo- curred during the recycling due to the leaching of the HPA
hexane and n-hexane with hydrogen peroxide at room from the support.
temperature. Tungstophosphoric acid (PW) supported on AC catalysts
were used to synthetize β-acetamido ketones by the Dakin–
West reaction (Scheme 19).75 PW/C catalysts, prepared by the
2.4 Heteropolyacid supported ACs
pore filling impregnation technique, showed high yields and
Catalysis based on heteropolyacids (HPAs) and their related better reusability versus the other supports used. Then, the
compounds is an important field in which new and promis- PW/C catalysts were used under solvent-free conditions to
ing developments are being carried out both at the research synthetize 1,4-dihydropyridines from various aldehydes,
and technological levels. Their highly acidic nature is very β-dicarbonyl compounds and amines,76 and in the condensa-
interesting in industrial reactions. Thus, they are used as an tion of aniline with ethyl acetoacetate to afford
industrial catalyst in alcohol dehydration, alkylation or esteri- β-enaminones.77 The PW/AC catalysts have also been used in
fication reactions. In the past decades, HPAs have attracted the acetylation of glycerol.78 In this last study, the catalytic
great interest of catalyst researchers because their acid–base activity increased with the amount of PW immobilized on the
and redox properties are widely used in heterogeneous cataly- AC, except for high loading of PW, likely due to some hin-
sis. HPAs are used as catalysts for organic synthesis processes drance in the porous system of the AC.
in industries related to fine chemicals, such as the flavor, More recently, HPAs have been supported on AC fibers
pharmaceutical and food industries. However, they are highly (ACF) as catalysts in the biodiesel synthesis.79 The use of ACF
soluble in polar media and it is often difficult to separate as a catalytic support in liquid reactions is more suitable
them from the reaction media. Therefore, a new series of cat- than conventional AC due to their particular features, such as
alysts have been developed by supporting HPAs on various smaller hydrodynamic resistance, fibrous shape, high mass
supports such as ACs. The impregnation of these supports transfer rates and easy removal from the reaction medium.
with HPAs significantly increases their surface area, which is On the other hand, Abdullah et al.80 implemented an
very important for heterogeneous catalysis processes. Izumi ultrasound-assisted biodiesel production process catalyzed by
and Urabe were pioneers in supporting HPAs on ACs to be AC-supported tungstophosphoric acid catalysts.
used as catalysts in the intermolecular dehydration of buta-
nol and t-butyl alcohol in the liquid phase.69 They proposed
that there is no loss of the active component during the reac- 2.5 Gold ACs
tion proving that AC is an excellent carrier to entrap HPAs. In the past two decades, gold catalysis has seen an exponen-
Later, Chimienti et al.70 prepared tungstophosphoric acid tial growth leading to the development of many synthetic
(TPA) and tungstosilicic acid (TSA) supported on AC catalysts transformations of considerable importance for the build-up
by equilibrium and incipient wetness impregnation tech- of complex molecular systems, both under homo- and hetero-
niques and tested them in the dehydration of isopropanol. geneous conditions. Supported gold-based catalysts have
The samples prepared by the incipient wetness method were proven important for both environmental requirements and
almost inactive for the isopropanol dehydration due to the chemical industrial applications and, in particular, for fine
presence of an HPA fraction weakly attached to the support chemical applications.81 Specifically, ACs are the most stud-
surface. Subsequent studies performed for the dehydration of ied carbon-based material as supports and several research
several alcohols over TPA and molybdophosphoric acid groups have demonstrated the activity of AC-supported Au
supported on AC catalysts showed that the alcohol conver- catalysts in various chemical reactions. Therefore, due to
sion depended on their molecular size.71 Moreover, selectivity their relevance and the growing number of publications in
to alkenes depended on the cyclodimer molecular size, whose the past years, this field deserves a separated subsection.
formation decreased with a larger dimer size. One of the pioneers in the preparation of gold supported AC
DuPont et al.72 showed that the acidic properties are catalysts was García et al.82 This research group carried out the
retained in heteropolyacid supported ACs. They proved that benzannulation reaction between 2-phenylethynylbenzaldehyde
HPA supported ACs are efficient catalysts for esterification re- and phenylacetylene over gold nanoparticles supported on AC
actions in the liquid phase.73 They realized that the activity (Au/AC) catalysts. The Au/AC catalysts had high selectivity at
loss increases with the surface area of the carbon support full conversion under the same reaction conditions as the
and, for a particular support, it decreases with the polyanion homogeneous catalysis with soluble AuCl3. The catalyst could
Scheme 18 Oxidation of cyclohexane to cyclohexanol and

cyclohexanone over goldĲIII) C-scorpionate complexes supported on Scheme 19 Synthesis of β-acetamido ketones over
carbon materials. tungstophosphoric acid (PW) supported on activated carbon (AC).
View Article Online
be reused up to four times without loss of activity or selectivity Gold supported AC catalysts have also been used in the oxi-
with minor leaching of the inactive gold species. dation reactions of carbohydrates and alcohols, among others.
The catalytic performance of gold supported on AC (Au/C) Okatsu et al.88 have reported for the first time that highly dis-
catalysts in hydrochlorination reactions has been widely in- persed Au nanoparticles on AC exhibited a relatively high cata-
vestigated. Several strategies have been considered in order lytic activity on the glucose oxidation reaction. They described
to improve the catalytic performance of the Au/C catalysts in that the Au nanoparticles could be deposited on AC directly
this reaction. Thus, Wittanadecha and coworkers83 prepared from the gold precursor compounds by a deposition reduction
Au/C catalysts by different methods, such as ultrasonic- method and, more effectively, by a solid grinding method.
Hermans et al.89 prepared Au/C and Au–Pd/C catalysts by an ad-
assisted, microwave-assisted, and conventional incipient wet-

ness impregnation techniques, to test them in the hydro- sorption method, optimizing the process by managing the pre-
chlorination of acetylene. The better results were obtained in cursor–support interactions. The bimetallic catalysts were more
the case of the Au/C catalysts prepared by the ultrasonic- active in glucose oxidation than their monometallic analogues,
assisted technique (conversion > 80% and a selectivity to vi- due to the synergetic effect between the Au and Pd metals. The
nyl chloride monomer of 99.5% after 20 h). The effect of pre- metal incorporation order, the oxidation state and the activat-
treatment seemed to influence the catalytic activity of the Au/ ing agent used also influenced the catalytic performance.
C catalysts. Thus, the presence of the Au3+ species on the cat- Gold catalysts seem to be more resistant to oxygen poison-
alyst surface led to the maximum initial catalyst activity. ing and selective for the oxidation of primary alcohols, such
On the other hand, Wang et al.84 studied the influence of as glycerol (Scheme 20). Demirel et al.90 reported the oxida-
different levels of oxygenated groups on the surface of Au/C tion of glycerol over gold supported on carbonaceous mate-
catalysts having similar textural parameters in acetylene rials showing that the textural properties of the support can
hydrochlorination. They concluded that phenol, ether, and influence the product distribution. Thus, gold nanoparticles
carbonyl groups on the AC surface are responsible for the cat- supported on CNTs displayed better activity and selectivity to
alytic activity and stability of the Au/C catalysts. Huang dihydroxyacetone than the gold supported on activated car-
et al.85 carried out the acetylene hydrochlorination over bon catalysts. Later, Rodrigues et al.91 performed the oxida-
TiO2–AuCl3/AC catalysts by the addition of TiO2 species to the tion of glycerol over gold catalysts prepared by using a set of
AuCl3/AC catalysts. It seems that the TiO2 species in the modified activated carbons with different levels of oxygenated
TiO2–AuCl3/AC catalysts relatively inhibited the reduction of functional groups on the surface, but with no significant dif-
Au3+ to Au0 and strengthened the adsorption of hydrogen ferences in their textural parameters. Thus, gold particles
chloride in acetylene hydrochlorination due to the strong with similar average sizes led to different performances: the
interaction between the Au3+ active sites and the TiO2 spe- presence of surface oxygenated acid groups inhibited the cat-
cies. Reduction of the Au3+ species to metallic Au0 species alytic activity, whereas basic oxygen-free supports led to more
was believed to be the predominant reason for the quick de- active catalysts. However, the presence of oxygenated groups
activation of the Au-based catalysts. on the AC support does not influence significantly the selec-
The support effect, as well as the introduction of a sec- tivities. Other research groups have prepared gold supported
ond metal, has been deeply investigated in order to increase on AC catalysts by the gold–sol method. The Au/AC catalysts
the catalytic performance of gold-supported AC catalysts. prepared by sol immobilization displayed a better gold dis-
Regarding that, Zhang et al.86 studied the ternary persion and a smaller gold particle size showing better cata-
Au–CoĲIII)–CuĲII) catalyst supported on spherical AC in the lytic activity in glycerol oxidation.92 On the other hand,
acetylene hydrochlorination. Its catalytic activity appeared Domínguez et al.93 reported gold nanoparticles supported on
to be due to the presence of the synergistic effects of CoĲIII) AC (Au/AC) as catalysts in the catalytic wet peroxide oxidation
and CuĲII) that enhanced the adsorption of hydrogen chlo- of phenolic wastewater. The catalyst suffers rapid deactiva-
ride on the catalysts, increasing the amount of the active tion but its activity can be completely restored by an oxidative
species Au+ and Au3+. The results obtained (99.7% acetylene thermal treatment at 200 °C.
conversion, 99.9% selectivity to vinyl chloride, and 6513 h Nevertheless, it seems that combinations of gold with plat-
of estimated lifetime) suggested the potential industrial ap- inum group metals have exhibited potential for industrial ap-
plications of this catalyst. Bonarowska et al.87 proved that plications, and in particular, Pd–Au catalysts supported on
AC-supported Pd–Au catalysts were more active catalysts in
the hydrodechlorination of tetrachloromethane than the
monometallic Pd catalysts due to the synergistic effects ob-
served for the Pd–Au alloys. The Pd–Au intermixing was cru-
cial to obtain the desired synergistic effect. The improved
deactivation resistance associated with the reduced reten-
tion of the surface chlorine and carbonaceous species dur-
ing hydrodechlorination was responsible for the higher total
activity and better selectivity towards the hydrocarbon Scheme 20 Glycerol oxidation over gold supported on carbonaceous
products. materials.
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carbon for liquid phase oxidations and hydrogenations, as these characteristics together with its high specific surface
displayed below. It was shown that alloying Pd to Au nano- area and the possibility to interact with organic molecules
particles led to a significant enhancement of the catalytic ac- through π-stacking interactions make graphene as the cur-
tivity in the selective oxidation of glycerol, also increasing the rent support key material in the development of superior
durability of the catalyst.94 Dimitratos et al.95 carried out the heterogeneous catalytic systems.97 However, stabilization and
liquid phase oxidation of glycerol over gold–palladium nano- functionalization of graphene via modification of materials
particles supported on AC. The control of selectivity could be are necessary to avoid the known undesired aggregation
possible when the appropriate reaction conditions were se- (stacked graphitic structures), which in turn extend its appli-
lected, while the activity was strongly dependent on the cata- cations. These materials have been successfully tested,
lyst amount and the concentration of the base. Szumelda mainly, in catalytic hydrogenation, oxidation, and coupling
et al.96 performed the hydrogenation of cinnamaldehyde in reactions.
the liquid phase on AC PdAu catalysts (Scheme 21). Appar- The activity and selectivity of Au-based catalysts for a variety
ently, the Au content affected both the activity and selectivity of important synthetic reactions are widely recognized. This
of the activated carbon PdAu catalysts for cinnamaldehyde fact combined with the unique properties of graphene has
hydrogenation. The surface composition of these catalysts contributed to the development of new Au nanocomposites
and the geometric and electronic modifications of the Pd with improved catalytic behavior. In this respect, Xie et al.98
sites due to the Pd–Au interactions seemed to influence the reported the synthesis of Au-based graphene catalysts for the
activity and selectivity of the reaction. oxidation of alcohols to aldehydes/ketones. Au nanoparticles
(2–4 nm) were deposited on nitrogen-doped graphene nano-
3. Miscellaneous sheets (NG) via the direct simple reduction method. The nitro-
gen atom doped graphene nanosheets (NG) play an essential
As anticipated, the application of different nanocarbon gener- role in stabilizing the Au nanoparticles serving as the anchor-
ations in catalysis is a hot topic. In the following sections, we ing sites for the Au seeds. Based on the studies carried out by
have summarized the most relevant advances in this promis- some authors, a plausible mechanism was proposed for gold
ing research field. We have focused on significant members formation on NG where tetrachloroaurate(III) ions, AuCl4−, are
of a group of carbon nanoallotropes with sp2 carbon atoms firstly adsorbed at the N doping sites, and then reduced to
arranged in a hexagonal network. This common structure Au(0) nuclei by using NaBH4. The remaining AuCl4− could be
means that they all have some common properties, although adsorbed endlessly on the surface of the as-formed gold nuclei
they also have significant differences due to their different and reduced to Au(0), leading to the growth of a gold nucleus,
sizes and shapes. The simplest and most basic representative or adsorbed on a new reactive site and directly reduced to
of this group is graphene, whereas carbon nanofibers (CNFs) Au(0), forming a new nucleus (Fig. 3). In general, the average
and carbon nanotubes (CNTs) consist of stacked and curved size of the gold supported nanoparticles did not vary with in-
graphene sheets arranged in various ways. creasing gold loading. The catalytic behavior of this composite
was evaluated in the aerobic selective oxidation of benzylic al-
3.1 Graphene cohols, at 343 K under aerobic conditions, in the presence of
Graphene has recently attracted much more attention in the H2O. The initial reaction of benzyl oxidation catalyzed by the
scientific community due to its exceptional properties. In Au/NG composites was notably higher than that over the Au/
comparison with the other carbon allotropes, this nano- graphene catalysts.
material offers the greatest intrinsic carrier mobility at room Porous graphene oxide (p-GO) as a metal-free catalyst was
temperature, with a perfect atomic lattice and excellent me- recently reported by Su et al.99 for the oxidative coupling of pri-
chanical, thermal, electrical and optical properties. All of mary amines under aerobic conditions in tandem to produce a
series of valuable products such as α-aminophosphonates,
α-aminonitriles, and polycyclic heterocompounds. The authors
described for the first time a bifunctional catalyst, Pd@p-GO,
in which p-GO was decorated with Pd nanoparticles, able to si-
multaneously activate molecular oxygen and hydrogen for the
tandem oxidation and hydrogenation reactions in the
N-alkylation of primary amines, under mild conditions
(Scheme 22).
The tentative mechanism for the tandem catalysis by
Pd@p-GO consisted of i) the oxidative coupling reaction of
the primary amine on the active defect sites producing the
imine intermediates, and ii) the activation of the molecular
hydrogen, in the presence of the Pd nanocatalyst, and the
Scheme 21 Hydrogenation of cinnamaldehyde over PdAu supported transfer to the imine intermediates leading to the secondary
on carbonaceous material catalysts. amine products (Fig. 4) with good to excellent yields.
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Fig. 4 Proposed mechanism for the Pd@p-GO bifunctional catalytic

system.
Fig. 3 Proposed mechanism of gold formation on nitrogen doped
graphene. Reprinted with permission from ref. 98. Copyright © 2012
RSC.
hybrid catalyst showed not only the best catalytic perfor-

mance (90% conversion after 150 min of reaction time) but
Verma et al.100 reported a magnetically separable GO- also its activity, being slightly superior to that of the related
based catalyst, containing a uniform distribution of iron acetoxy-functionalized NHC iridium homogeneous ones. The
nanoparticles, for the oxidative cyanation of tertiary amines. presence of remaining oxygen functional groups on the hy-
Characterization of the composite by using the XRD and XPS brid catalyst based on GO, as competitive sites, could be re-
techniques clearly indicated that the support was enriched sponsible for the lower catalytic performance observed.
with the crystalline Fe/FeO phases without any evidence of The non-covalent interactions between graphene and poly-
the presence of the Fe2O3 phase; the layer of FeO was present aromatic hydrocarbons such as pyrene-derivatives emerge as
on the surface of the Fe(0) nanoparticles. The catalyst was an interesting, useful and alternative synthetic approach for
tested in the oxidative cyanation of a variety of tertiary the preparation of heterogeneous graphene-based catalysts.
amines, in the presence of H2O2 and sodium cyanide, in This synthetic route allows the introduction of the appropri-
acetic acid, yielding the corresponding α-aminonitriles with ate functional groups over the nanocarbon without affecting
good to excellent yields (up to 77%) (Scheme 23). The active its electronic network. In this context, Sabater et al.102 de-
species for the reaction were the FeĲII) species and not the scribed new nanostructured graphitic materials based on Pd
metallic iron. and Ru complexes, prepared from an imidazolium salt
As mentioned above, the most frequently used synthetic substituted with pyrene moieties, which were immobilized
approach for the homogeneous catalyst immobilization con- onto the graphene oxide (rGO) surface by π-stacking interac-
sists of the covalent bond formation between the solid sup- tions (Scheme 25). The catalytic behavior of these nano-
port and the ligand, implying the necessary functionalization structured hybrid materials was investigated in the
of both species and originating changes in chemical reactiv- ruthenium-catalyzed oxidation of alcohols and in the
ity. To this end, more recently Blanco et al.101 reported new, palladium-mediated hydrogenation of alkenes and nitro-
stable and reusable hybrid graphene-based-Ir-NHC materials arenes (Schemes 26–28) giving rise to higher activities than
(where NHC is N-heterocyclic carbene) (Fig. 5) for the the related homogeneous catalysts. The catalysts therein
hydrogen-transfer reduction of cyclohexanone to reported were recycled 10 times without loss of activity.
cyclohexanol. Cross-coupling reactions, such as the Heck, Suzuki and
These nanohybrids were prepared by the covalent Sonogashira reactions, were also investigated in the presence
functionalization of graphene oxide (GO) or thermally re- of metal nanoparticles supported over GO. Concerning that,
duced graphene oxide (TRGO) as follows i) a reaction with Moussa et al.103 developed a new family of highly active Pd
p-nitrophenylchloroformate, through their OH− surface nanoparticle catalysts supported on partially reduced
groups, ii) subsequent covalent anchoring of a hydroxy- graphene oxide nanosheets for these types of transformations.
functionalized imidazolium salt and, finally, iii) by a subse- Pd nanoparticles of different sizes were supported on partially
quent reaction with [IrĲl-OMe)Ĳcod)]2. These catalysts were ac- reduced graphene nanosheets (Pd/PRGO) by pulsed laser irra-
tive in the heterogeneous hydrogen-transfer reduction of diation of aqueous solutions of GO and palladium ions
cyclohexanone to cyclohexanol using 2-propanol/KOH as the
hydrogen source (Scheme 24). The TRGO–NHC–iridium
Scheme 22 Simultaneous activation of molecular oxygen and Scheme 23 Oxidative cyanation of tertiary amines catalyzed by a
hydrogen. iron–graphene nanocomposite.
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Scheme 26 Alkene hydrogenation using molecular hydrogen.

Fig. 5 Hybrid graphene-based Ir–NHC materials.
tolerance. Furthermore, this nanocarbon was a very efficient

catalyst for the quantitative synthesis of the core constituents
of top selling drugs, such as boscalid, telmisartan, and bio-
logically active GSK376501A (Fig. 6).
Scheme 24 Hydrogen transfer reduction of cyclohexanone to
Shaabani et al.105 reported a highly active and reusable
cyclohexanol. catalyst based on PdCo bimetallic nanoparticles supported
on polypropylenimine (PPI)-grafted graphene for the carbon–
carbon cross-coupling Sonogashira reactions, under solvent-
free conditions, at room temperature, and ultrasound irradia-
without the use of chemical reducing or capping agents. This tion. The PPI dendrimer was synthesized by using a divergent
process provoked the formation of multiple defects on the sur- strategy from malononitrile functionalized graphene as fol-
face of the PRGO, providing an excellent environment for an- lows: i) reduction of CN to amine groups, ii) Michael addition
choring the Pd nanoparticles. These metal nanocarbons were of the amine groups to acrylonitrile and iii) subsequent re-
active for the Suzuki cross coupling reactions affording biphe- duction of the introduced CN groups. Finally, PdCo alloy
nyl with an excellent yield (ranging from 80 to 95% after 8 h of nanoparticles were then attached via a co-complexation
reaction time), at room temperature, even when the catalyst method. The catalytic activity of the bimetallic catalyst was
loading was decreased to 0.008 mol%. The reaction was sur- notably higher than that observed for the individual nanopar-
prisingly fast working at 120 °C under MW irradiation (quanti- ticle (Pd or Co) catalysts (Scheme 30).
tative yield in only 5 min). The catalysts under study were also A similar strategy for the in situ growth of palladium and
active in the Heck and Sonogashira cross coupling reactions, the assembly of Fe3O4 nanoparticles on reduced graphene ox-
under MW irradiation, leading to the corresponding biaryls ide (rGO) dendrimers has been reported by Liu et al.106 Pd/
with excellent yields (Scheme 29). Fe3O4/PEI/rGO (where PEI is polyethyleneimine) is a highly
In the same line, Santra et al.104 reported the anchoring of active and reusable catalyst in the Tsuji–Trost reaction
Pd nanoparticles onto the GO sheet by pyrolysis, without (Scheme 31). Pd/Fe3O4/PEI/rGO is easily removed from the re-
using any external reducing agent, as a recyclable catalyst for action crude mixture with the simple application of an exter-
the synthesis of biaryl cores for the Suzuki–Miyaura coupling nal magnetic field, and exhibiting the best catalytic perfor-
reaction. The scope of the methodology was explored by syn- mance when compared with the corresponding monometallic
thesizing biaryls with a wide variety of functional group catalysts.
Scheme 25 Immobilization of Pd and Ru complexes, prepared from an imidazolium salt substituted with pyrene moieties, onto the graphene
oxide (rGO) surface.
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graphene undergo spontaneous oxidation to render oriented

(2 0 0) Cu2O nanoplatelets on few-layered graphene. These
films containing oriented Cu2O exhibit catalyst turnover
numbers that can be three orders of magnitude higher for
Scheme 27 Nitro reduction using molecular hydrogen. the Ullmann-type coupling, dehydrogenative coupling of di-
methylphenylsilane with n-butanol and C–N cross-coupling
than those of the analogous unoriented graphene-supported
copperĲI) oxide nanoplatelets.107
Although the use of graphene has this successful progress,

some key issues still need to be addressed on the way for-
ward. Thus, the preparation of perfect graphene sheets lags
far behind the great demands on their practical applications.
The recent exfoliation method108 can hardly provide a uni-
Scheme 28 Oxidant free dehydrogenation of alcohols. form and clean single layer of graphene, while the commonly
used oxidation–reduction pathway is bothered with the intro-
duction of defects and decrease in the transport properties.
As a consequence, the lack of an effective way to ideal
graphene has gradually become one of the biggest bottle-
necks for making further improvement in the performance of
the assembled structures.
3.2 Nanofibers
Carbon nanofibers (CNFs) are a noncontinuous 1D carbon
nanoallotrope of cylindrical or conical shape, consisting of
stacked and curved graphene sheets arranged in various
ways.109 They were identified and extensively studied long
back before the discovery CNTs. They are frequently de-
scribed as sp2-based linear filaments with a diameter ranging
Scheme 29 Heck and Sonogashira coupling reactions catalyzed by from 50 to 200 nm and a high aspect ratio exceeding 100.
Pd/PRGO. Depending on the internal structure of the CNF (i.e., the way
the graphene sheets are arranged), the types of CNF are i)
platelet-type (p-CNF), ii) ribbon or tubular-type (t-CNF), and
iii) fishbone-type CNF (f-CNF)110 with the graphite layers per-
pendicular, parallel, and tilted to the principal axis, respec-
tively (Fig. 7).
Moreover, three topological structures have been proposed
to represent the f-CNF morphology: i) the stacked-up and ii)
cone-stacked CNFs, with a similar structure composed of
truncated cones arranged to leave a hollow core, and iii)
cone-helix CNFs with a graphite layer forming a continuous
helix–spiral architecture and with an internal hollow core.
The orientation of the graphite layers, and hence the basal-
to-edge surface area ratio, has been found to have significant
effects on the catalytic activity and selectivity of CNFs.111 α is
defined as the position of the graphene sheet near the
Fig. 6 Core constituents (in blue) of top selling drugs: boscalid,

telmisartan, and GSK376501A.
Recently, the catalytic activity as a function of metal nano-

particle orientation on graphene substrates has been Scheme 30 Sonogashira cross coupling catalyzed by PdCo bimetallic
highlighted. Thus, oriented (1 1 1) copper nanoplatelets on nanoparticles supported on polypropylenimine (PPI)-grafted graphene.
View Article Online
The use of CNFs as catalyst supports and/or directly as

catalysts has been an active topic of research118 since the
first report published in 1994.114 Their properties can exert
a significant impact compared to the traditional carbon or
oxide supports. The following characteristics make CNFs at-
tractive as catalysts and catalyst supports: i) the presence of
a large number of edges in CNFs provides anchoring sites
for catalyst precursors. Modern techniques have made it
possible to control the surface geometric structure and sur-

face chemistry of CNFs,119 which opens up opportunities to
tailor the properties of both the CNF surface and its
Scheme 31 Tsuji–Trost reaction catalyzed by Pd/Fe3O4/PEI/rGO. supported metal nanoparticles; ii) the surface properties of
CNFs (and CNTs) can be easily adjusted by surface oxida-
tion, foreign-ion doping (i.e., nitrogen or boron), or by using
sidewall surface with respect to the axis of the CNF and this the confinement effect so as to fulfill the different require-
angle determines the physicochemical properties of the ments for different applications; iii) as catalyst supports,
CNFs. Thus, CNFs with cone and tilted-graphene sheet motifs CNFs offer some unique advantages over the more tradi-
are characterized with α > 0. tional materials, such as alumina or silica, because CNFs
CNFs have unique features and specific characteristics, such (and CNTs) exhibit high surface area and are also heat and
as fibrous structures, high resistance to strong acids and bases, electrical crystallite conductors, so strong interactions can
porosity, high electric conductivity (similar to graphite), high be formed between the metal atoms and the CNTs/CNFs. As
surface area (80–200 m2 g−1), well-defined nanostructures, easily a consequence, modification of the morphological charac-
tuned mesoporous properties, and high mechanical strength.112 teristics of the catalyst particles could give rise to unex-
These interesting properties of these 1D-structured carbon pected activity and selectivity patterns. The combination of
nanomaterials have been intensively reviewed113 and exploited structural and electrical properties makes CNTs/CNFs very
in many applications, such as catalysts and catalyst support ma- attractive as candidates for exploitation both as catalysts
terials,109,114 functional components of electronic devices (bio- and catalyst supports; iv) CNTs and CNFs mostly consist of
sensors, anodes in lithium ion batteries, electrodes in fuel mesopores with large external surfaces, which make them
cells),115 materials for gas storage,116 and polymer additives in superior supports for fast reactions in the gas and liquid
the formation of composites to improve their chemical, thermal, phases and for complex reactions in which the products are
and electrical features.117 Herein, we focus on their use in the not chemically stable. Compared to traditional carbon mate-
catalysis field. rials, in particular to AC, mass-transfer limitations during
the reaction can be reduced so that the activity and selectiv-
ity would be enhanced.
Their graphitic structure leads to metal–support interac-
tions and an electron transfer between the metal particles
and the graphitic support (electronic perturbation) which can
improve the catalytic activity/selectivity. The CNF structure
has a remarkable influence on the interactions, due to the
different edge-site-to-basal-plane ratios, and the edge sites
and defects form much stronger bonds with the metals, thus
leading to strong interactions. The interactions of metals
with CNFs follow the order: platelets > fishbones > tubes.
Metal/CNF surface interactions influence the dispersion, sta-
bility, as well as the redox potential of the metal, which can
be tailored to improve the activity for catalytic reactions that
involve redox cycles.112,120
The effective utilization of the high-surface-area meso-
porous structure of 1D carbon nanomaterials (CNTs and
CNFs) in catalysis through improved dispersion of the metal
or metal-oxide nanoparticles has been widely explored in the
literature121 and some key examples are shown in Table 2.
High selectivities have been observed in these catalytic sys-
Fig. 7 Schematic representations of CNFs with different basal-to-
edge surface area ratios: (a) platelet-type CNF, (b) ribbon/tubular-type
tems displaying different metal–support interactions and/or
CNF, and (c) fishbone-type CNF. Adapted from ref. 111 with permission change transfer phenomena compared to those on other sup-
from Elsevier. Copyright © 2012. ports, such as ACs or alumina.
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3.3 Carbon Nanotubes most common examples.144 As a result of the differences be-
tween the ratios of the edge planes to the basal planes, CNTs
CNTs and CNFs show notably different nanostructures and are thus differentiated from CNFs in key electronic properties
properties, despite both containing curved sp2-hybridized car- and surface (re)activity behavior.145
bon atoms. The main difference involves the configuration of Since the discovery of multi-wall carbon nanotubes
the underlying planes that are created by the alignment of the (MWNT) by Iijima,146 CNTs have become one of the most ac-
carbon atoms. CNTs display an axial alignment of the concen- tive fields of nanoscience and nanotechnology due to their
tric cylindrical planes that are mainly composed of hexagonal exceptional properties that make them suitable for many po-
substructures. In this sense, CNTs can be sub-classified into tential applications as polymer reinforcements for compos-
single-walled carbon nanotubes (SWCNTs, diameters of around ites or breakthrough materials for energy storage, electronics
0.4–2 nm and are several micrometers long, with an empty and catalysis.
internal space), and multi-walled carbon nanotubes (MWCNTs) Due to the high strength of the covalent CC bonds be-
by considering the number of axially aligned cylindrical tubes. tween adjacent sp2 carbon atoms, CNTs are the strongest yet
The aspect ratio (i.e., length-to-diameter ratio) of carbon nano- known materials with a high flexibility. SWNTs have shown re-
tubes frequently exceeds 10 000, and thus, they are regarded as markable superplasticity, becoming nearly 280% longer and 15
the most anisotropic materials ever produced. Apart from the times narrower before breaking, which is explained in terms
diameter and the length, chirality (the angle between the hexa- of the nucleation and motion of kinks in the structure.147,148
gons and the nanotube axis) is another key parameter of the The electronic properties of SWNTs are mainly governed
carbon nanotubes. Depending on the chirality, the carbon by two factors: the tube diameter and the helicity, which is
atoms around the nanotube circumference can be arranged in defined by the way in which the graphene layer is rolled
several ways: the armchair, zigzag, and chiral patterns are the up149 (armchair, zigzag or chiral). In particular, armchair
Table 2 Representative examples of metal–CNF catalysts
Catalyst Reaction Ref. Results

Hydrogenation
Ni/CNF Alkene hydrogenations 122 Reaction sensitive to the nature of the metal–support interaction
Rh/CNF Cyclohexene 123 Activity independent of the nanoparticle size. Influence of oxygen-containing spe-
cies present on the surfaces of the support
Ru/CNF Arene 124 Excellent catalytic activity
Pd/CNF Phenol 125 Complete hydrogenation to alcohol
Ni/CNF Crotonaldehyde 126 Formation of crotyl alcohol with higher selectivity than with γ-Al2O3
Pd/CNF Cinnamaldehyde 127 Selective hydrogenation of CC. More active than Pd/AC
Ru/CNF Cinnamaldehyde 128 Crucial role of cinnamaldehyde adsorption on the support
Dehydrogenation
Pt/CNF Hydrogen production from 129 Performance strongly affected by the metal particle dispersion
decaline
Involving CO/H2 reactions
Co–Cu/CNF Alcohol synthesis 130 Selectivity towards the formation of higher alcohols (butanol)
Rh/CNF Hydroformylation of ethylene 131 Higher selectivity than Rh/SiO2, probably due to the hexagonal shape of the
rhodium crystallites
Ru/CNF and Ammonia synthesis 132 More active than AC due to the high purity of the support
Ru–Ba/CNF
Biomass conversion
Ru/CNF Hydrogenolysis of sorbitol to 133 Better behavior than Ru/AC due to the higher Ru dispersion on CNF
glycols
Ni/CNF Hydrolytic hydrogenation of 134 Appropriate catalyst balance between Ni dispersion and hydrogenation capacity,
cellulose to C6 sugar alcohols and the number of acidic surface-oxygen groups responsible for the acid-catalyzed
hydrolysis
Oxidation reactions
Pt/S–CNFs Glycerol with molecular oxygen 135 Selective formation of glycerin acid in a base-free aqueous solution
Cu/CNF, Ni/CNF Ethylene glycol and glycerol to 136 Under anaerobic aqueous conditions
organic acids
RuO2/CNF Alcohols to aldehydes 137 Superiority over Ru–ACs under aerobic conditions; high metal dispersion
Other reactions
Pt/CNF Skeletal n-hexane reaction 138 Better activity and isomer formation on Pt/f-CNF than on Pt/p-CNF
La2O3/CNF Self-condensation reaction of 139 Superior catalytic activity to the optimized bulk La2O3
acetone to diacetone
LaCl3/CNF Dechlorination of hydrocarbons 140
Pd/CNF Heck reaction 141 The activity increased exponentially with a decrease in the Pd particle size, low
sensitivity towards oxygen, and high stability in multi-cycles
Ir/f-CNF Hydrazine decomposition 142 Better performance than a commercial Ir/Al2O3 catalyst
Hydrotalcites/CNF M1BK synthesis 143 Specific activity four times higher than that of the unsupported catalyst
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SWNTs are metallic and the zigzag ones display a semi- use. Therefore, CNTs generally need to undergo chemical
conductor behavior. The rolling up of the graphene layers functionalization to enhance their solubility in various sol-
can vary along the different walls of a single MWNT, so a fine vents and to produce novel hybrid materials for practical
prediction of the electronic properties is more difficult. applications.157
CNTs present specific adsorption properties when com- Doping of CNTs with nitrogen improves the physical prop-
pared to graphite or to AC, mainly due to their peculiar mor- erties of CNTs by introducing surface defects into the
phology, the role of defects, opening/closing of the tubes, graphene structure of N-CNTs. Such surface defects promote
chemical purification or the presence of impurities as catalyst N-CNT surface wetting resulting in increased catalytic activ-
ity.158 However, it should be noted that the available types of
particles. Other important factors in the final activity and re-

producibility of the catalytic system are the resistance to catalyst preparation depend on the surface properties. For in-
abrasion and dimensional and thermal stabilities. In particu- stance, Pt particles are uniformly dispersed over these mate-
lar, and analogously to CNFs, they could replace ACs in rials and they have a smaller average particle size than on
liquid-phase reactions since the properties of ACs are still dif- non-nitrogen-doped carbon supports. This dispersion helps
ficult to control and their microporosity has often slowed to increase the catalytic activity of the metal in various reac-
down catalyst development. tions, such as oxygen-reduction reactions,159 both hydrogen-
CNTs are not dispersible in organic solvents or water and oxidation and oxygen-reduction reactions in proton-exchange
are usually held strongly together in bundles by significant membrane fuel cells160 or the hydrogenation of
van der Waals interactions.150,151 A similar group of cylindri- nitroarenes.161
cal carbon nanostructures that have recently appeared in the The edge structure, with various edge-site-to-basal-plane
literature are referred to as bamboo-like CNTs due to the divi- ratios, and the functional groups on the edge sites have a
sion of their internal spaces into small cavities similar to significant influence on the electron localization and, thus,
those found in bamboo.152 the proton affinity of these materials. Oxygen-free or
The syntheses of CNTs have been intensively reviewed,153 N-doped edge sites have a strong basicity, which contribute
although a general principle for the rational design of carbon to better anchoring of the metal nanoparticles and improve
nanomaterials in a controlled manner is yet to be the catalytic performance of these carbon materials.162 Ac-
established. cordingly, the improved chemical and electrical properties
In contrast to porous carbons, the large surface areas of of N-doped CNTs have been observed which result in the
the external surfaces of CNTs are ideal for the immobilization activation of the metal catalyst163 and enhancement of the
of metallic or metal oxide nanoparticles that are used in cata- binding energy between the N-CNTs and the metal cata-
lytic systems, since they allow better contact between the re- lysts.164 For instance, Nyamori et al.165 have recently
actant and the catalytic component. Electronic effects that reported that pyrrolic Pd/N-CNTs exhibited high yields and
are derived from interactions between the metal and the sup- a higher selectivity towards aminobenzophenone in the hy-
port can endow the catalyst particles with unusual properties. drogenation of nitrobenzophenone than Pd on carbon
The deposition of metal nanoparticles on CNTs has been nanotubes and Pd on AC (Scheme 32). The enhanced selec-
reviewed extensively by several groups.154 tivity towards nitroreduction over p-benzylaniline observed
First-principles electronic-structure calculations indicate with Pd/N-CNTs was attributed to the promoting effect of
that the energy barrier of metal–atom diffusion is much pyrrolic-N.
lower on the CNT sidewall than on the CNF edge.155 Thus, There is a large potential for the development and applica-
metal–catalyst agglomeration occurs very readily on the CNT tion of an organic polymer with tailored physical and chemi-
surface and causes low metal dispersion. These different fea- cal properties in both selective catalysis and functional mate-
tures in CNTs and CNFs have consequences on their catalytic rials science.166 Therefore, to combine the advantages of
properties if they are used as catalyst supports.113 polymers (nitrogen-containing polymers) and CNTs, much ef-
In parallel to the growing knowledge on the synthesis and fort has been put in polymer/CNT composite materials. Thus,
understanding of nanocarbon materials, their use as ad- for instance, the composite material polyĲ4-vinylpyridine)-
vanced catalysts moved to more rational bases. As noted functionalized carbon nanotubes (PVP/CNT), through the for-
above for CNFs, the engineering of CNTs makes it possible to mation of the coordinative bond N:→Ru3+, shows interesting
control the arrangement of the carbon atoms, providing op- properties. The ruthenium complex immobilized on PVP/CNT
portunities to tailor the properties of both the CNT surface (Ru-PVP/CNT) catalyst reveals excellent catalytic performance
and its supported metal nanoparticles. Table 3 shows their towards selective aerobic oxidation of biomass-based
relevant applications as supports in synthesis. 5-hydroxymethylfurfural to 2,5-diformylfuran167 (Fig. 8).
To improve the catalytic activity of CNTs, heteroatom- It has been recently realized that metal nanoparticles can
containing functional groups can be introduced onto the sur- be effectively stabilized against coalescence by encapsulation
face of CNTs. Thus, nitrogen, oxygen, phosphorous, sulphur within metal oxide layers, such as SiO2 shells. The catalytic
and boron can be used to modify the surface chemistry of results showed that Pt@CNT/SiO2 was active for the hydroge-
CNTs.156 In addition, the lack of solubility and the difficult nation of nitrobenzene with a very high activity comparable
manipulation of CNTs in most solvents have limited their to that of Pt@CNT.168
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Table 3 Representative examples of metal–CNT catalysts
Catalyst Reaction Reference Results

Hydrogenation
Pd/MWNT 1-Octyne 169 High stability
Pt/CNT Nitrobenzene 170 Excellent activity highly because of the dispersed Pt and the mesoporous
structure of the acid-oxidized CNT-supported Pt catalyst
Pt@CNT/SiO2 Nitrobenzene 168 Very high activity comparable to that of Pt@CNT
Pd/N-CNTs Nitrobenzophenone 165 Higher selectivity to aminobenzophenone than Pd on CNTs and Pd on AC
due to the promoting effect of pyrrolic-N
Pt/SWNT Prenal (3-methyl-2-butenal) 171 Active and selective

to prenol (3-methyl-2-butenol)
Co–Pt/SWNT Cinnamaldehyde 172 High activity and selective hydrogenation to cinnamyl alcohol due to the
mesoporous structure
Ru–Pt/MWNT Cinnamaldehyde 173 Mesoporous nanostructured support makes mass-transfer limitations less
significant and gives much higher activities. Higher selectivity than that
obtained with the monometallic systems.
Rh/MWNT Cinnamaldehyde 174 High selectivity and catalytic activity three times higher than the
corresponding Rh/C* catalyst
Dehydrogenation
Co/MWNT Cyclohexanol to cyclohexanone 175 Activity and selectivity towards cyclohexanone slightly higher than on Co/C*
CeO2/CNT Ethylbenzene to styrene 176 Showed an important confinement effect. Shorter CNTs filled with CeO2
exhibit higher catalytic activities due to the decreasing diffusion resistance
of the reactants and products in the CNT channels
Rh/MWNT Hydroformylation of hex-1-ene 174b More active than a Rh/C* catalyst
[HRhĲCO)ĲPPh3)3]/ Hydroformylation of propylene 177 Higher conversion and regioselectivity towards n-butyraldehyde than on
MWNT similar systems on AC, carbon molecular sieves and silica
CO/H2 reactions
Ru/MWNT Ammonia synthesis 178 Potassium promoted ruthenium catalysts supported on MWNT were much
more active than their counterparts deposited on graphite or fullerenes, due
to the higher surface area of the nanotubes that allows a better dispersion of
the metallic phase and to the electronic properties of this support that could
enhance the electron transfer from potassium to ruthenium
Biomass conversion
Ru/CNT Cellulose to C2–C6 polyols 179 The CNTs promote the hydrolysis of cellulose into a reduced sugar
Ru–PVP/CNT Oxidation of 5-hydroxymethylfurfural 167 Excellent catalytic performance and selectivity
to 2,5-diformylfuran
Ni/MWNT Pyrolysis of bio-oil 180 The uniform and narrow distribution of small Ni particles on the CNTs
lead to excellent low-temperature reforming of oxygenated organic
compounds in bio-oil
Au/MWNT Oxidation of glycerol 181 High selectivity for the oxidation of the secondary hydroxyl group to form
dihydroxyacetone, independent of the preparation method
Mo2C/CNT Hydrogenation of levulinic acid 182 When the carbide nanoparticles are positioned within the carbon
to γ-valerolactone nanotubes, conversions and selectivities are above 90%
Oxidation reactions
Pt/MWNT MeOH oxidation 183 Better performance than Pt-on-carbon-black, due to its large external
surface area and crystalline structure
Pd/MnOx/CNT Alcohol oxidations 184 The catalytic activity correlated with MnOx loading, indicating the important role
of manganese oxide in tuning the properties of the Pd catalytically active sites
W/MWNT Epoxidation of alkenes 185 WĲCO)6 supported on MWCNTs modified with 1,2-diaminobenzene is an
efficient catalyst for a wide range of linear and cyclic alkenes
Pt/CNT, Cu/CNT, Aniline oxidation 186 High external surface area and the absence of micropores provide an
Ru/CNT efficient surface contact between an aniline molecule and the active sites
Other reactions
Co/MWNT under Synthesis of mono- and 187 Excellent catalytic performance
sonication disubstituted
dihydroquinazolinones
through three-component
condensation
Pd/CNT Cross-coupling, 188 Pd nanoparticles deposited on MWNT possess the most functional
Suzuki–Miyaura catalytic properties, with optimum activity, stability and recyclability
in a range of cross-coupling reactions
Pd/MWNT Hydrodehalogenation of 189 The CNTs could significantly influence the catalytic activities of the
aryl halides CNT-supported metal catalysts
On other hand, it is known that the well-defined channels on the catalytic performance. Recent results have shown that
of CNTs can be used to introduce metallic and metal oxide encapsulated nanoparticles inside CNT channels have better
nanoparticles into the CNT cavity and investigate their effects catalytic performance compared to those on conventional
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Of growing interest also is the area of the designing nano-

carbon–nanocarbon hybrids and hierarchical systems gener-
ated by combining different carbon nanostructures, such as
functionalized fullerenes linked to CNTs (nanobuds), in order
to develop multifunctional superstructures.195–198 In this
Scheme 32 Hydrogenation of nitrobenzophenone over pyrrolic Pd/N-
CNTs. sense, CNT-based aerogels,199 a novel approach to develop
CNT networks, are promising for catalysis, serving as either
scaffolds or as the catalysts themselves. The rational use of
CNT-based aerogels as supports to load catalytic matter can

catalysts.118b,190 The confinement of nanoparticles inside the create high-performance catalysts.200
CNTs and their catalytic applications have been recently Unlike traditional catalysts where the reaction only occurs
reviewed by Pan and Bao.191 For instance, combined DFT in- at the external surface, the aerogel-supported metal catalyst
vestigations, CO adsorption, and ammonia synthesis have allows a “bulk phase” catalysis throughout the gel network
consistently indicated that the electron density of Ru parti- because of its porous structure.201 In summary, the combina-
cles outside the CNTs is higher than those confined inside tion of carbon nanostructures and different nanoscopic spe-
the CNTs.192 This difference is ascribed to the curvature of cies within a composite material is expected to result in the
the graphene sheet and to the higher energy density of enhancement of their functional properties and can lead to
graphene on the outside than on the inside of the CNTs. Am- new synergistic effects.202
monia synthesis193 and decomposition194 have been used as
probe reactions to investigate the electronic properties of Ru
nanoparticles on and inside the CNTs, because the adsorp- 4. Concluding remarks and future
tion and recombination of N atoms are normally very sensi- perspectives
tive to the electronic properties of the metallic nanoparticles.
The turnover frequencies (TOFs) of ammonia synthesis over Catalytic processes are involved in more than 90% of the
Ru-out were much higher than on Ru-in. world chemical manufacturing processes. The activity and se-
It has also been recognized that the electron densities of lectivity of a catalyst are often conditioned by its surface area,
the graphene sheets inside and outside the CNTs influence porosity, inertness, surface chemistry, purity, and cost effec-
the interactions of metal oxides with CNTs. It is much easier tiveness. However, the mechanical stability is also an impor-
to reduce the metal oxides inside the CNTs than on the out- tant parameter to be considered for the possible recyclability
side, due to different interactions.190,191 of the catalyst. Besides these requirements, carbon materials
Additionally, improved selectivity towards the desired additionally offer the possibility of easy tuning their surface
product when metal/CNT catalysts are used can also be at- chemistry, by using chemical and thermal post-modifications
tributed to nano-confinement of the substrate molecule in- followed by functionalization, or by employing the appropri-
fused into the CNTs.195 The confinement mainly modifies ate synthetic approaches. Nevertheless, carbon supports also
the electronic properties of the active phase, promotes the represent some disadvantages: they can be easily gasified,
dox properties of metal oxides and improves the states of which makes them difficult to use in high temperature hy-
gas-phase reactants inside CNTs during catalytic reactions. drogenation and oxidation reactions, and their reproducibil-
Nevertheless, due to synthetic difficulty, the confinement ef- ity can be poor, especially the activated carbon-based cata-
fect of CNT channels for these materials is limitedly applied lysts, since different batches of the same material can
in the catalytic reactions. contain varying ash amounts.
Porous carbons, particularly ACs, are considered versatile
and low cost catalysts and supports of the active phases with
an application in a wide variety of organic transformations
useful for the preparation of valuable products. The under-
standing of the surface chemistry of carbon materials is an
important issue in the application of carbon as catalysts or
even as supports for anchoring metal complexes or metal
nanoparticles, between other active species.5 Additionally,
functional groups over the surface of porous carbons can also
hinder the migration of metal crystallites when acting as sup-
ports and, therefore, minimize their agglomeration and
sintering. In fact, the performance of metal-supported cata-
lysts depends mainly on one side on the metal loading and
Fig. 8 Proposed structure of a Ru–PVP/CNT for the selective
on the other side of its distribution and dispersion on the
oxidation of 5-hydroxymethylfurfural. Reprinted with permission from support, with the size of the metal particles a key factor in
ref. 167. Copyright © 2015 RSC. determining the catalyst performance. Therefore, the
View Article Online
synthesis of highly dispersed metal catalysts depends on the an issue in comparison with “conventional” catalysts, as well
appropriate control of the surface chemistry. as the possibility to maximize their concentration to improve
The small-size limit of the supported metal particles is the catalyst productivity. Nowadays their production pro-
then a relevant aspect to be investigated in heterogeneous ca- cesses are more controlled, but it is still very difficult to
talysis. In this context, the single-atom catalysts (SAC) are maintain homogeneity in all the features, and a better under-
constituted by isolated metal atoms dispersed on supports.203 standing of the growth processes and catalyst synthesis are
SACs offer great potential by giving rise to high activity and needed. Moreover, critical aspects concerning standardiza-
selectivity while showing well-defined and uniform single- tion and toxicity206 should be addressed.
atom dispersion. To this end, a strong metal–support interac-

tion is the key to prevent aggregation of single atoms on the Acknowledgements
surface. Several supports such as metal oxides, metal sur-
faces, and graphene have been used for the preparation of This work has been supported by MICINN (projects CTQ2011-
SACs. In this sense, a few theoretical and experimental stud- 27935 and CTM2014-56668-R).
ies demonstrated that subnanometer-sized metal clusters can
sometimes increase the catalytic activity or selectivity when Notes and references
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Carbon-Based Materials

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Catalysis

Metal-supported carbon-based materials:

opportunities and challenges in the synthesis of

1. Introduction organic solids such as silica, zeolite and mesoporous mate-

Elena Pérez Mayoral studied Vanesa Calvino-Casilda obtained

Minireview Catalysis Science & Technology

carbon materials stand out for their industrial applications

tribute to the changes in their acid–base character and redox

Catalysis Science & Technology Minireview

2.1 Metal supported ACs

Minireview Catalysis Science & Technology

process in the compact reactor was more efficient than in the

catalytic activity of the system demonstrating that a compact

Scheme 4 Suzuki coupling reaction of 4′-chloroacetophenone cata-

Catalysis Science & Technology Minireview

Minireview Catalysis Science & Technology

AC catalysts for the oxidative carbonylation of phenol and

Catalysis Science & Technology Minireview

produced from ethylbenzene (EB) by dehydrogenation using

Minireview Catalysis Science & Technology

Catalysis Science & Technology Minireview

Scheme 13 Michael addition of imidazole and ethyl acrylate for the

2.3 Immobilized coordination complex over ACs

Immobilized coordination complex over a solid support is a

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Scheme 15 Claisen–Schmidt condensation of substituted

located inside the support porosity, where a minimum diam-

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Scheme 18 Oxidation of cyclohexane to cyclohexanol and

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assisted, microwave-assisted, and conventional incipient wet-

Catalysis Science & Technology Minireview

Minireview Catalysis Science & Technology

Fig. 4 Proposed mechanism for the Pd@p-GO bifunctional catalytic

hybrid catalyst showed not only the best catalytic perfor-

Catalysis Science & Technology Minireview

Scheme 26 Alkene hydrogenation using molecular hydrogen.

tolerance. Furthermore, this nanocarbon was a very efficient

Minireview Catalysis Science & Technology

graphene undergo spontaneous oxidation to render oriented

Although the use of graphene has this successful progress,

Fig. 6 Core constituents (in blue) of top selling drugs: boscalid,

Recently, the catalytic activity as a function of metal nano-

Catalysis Science & Technology Minireview

The use of CNFs as catalyst supports and/or directly as

possible to control the surface geometric structure and sur-

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Table 2 Representative examples of metal–CNF catalysts

Catalyst Reaction Ref. Results

Catalysis Science & Technology Minireview

particles. Other important factors in the final activity and re-

Minireview Catalysis Science & Technology

Table 3 Representative examples of metal–CNT catalysts

Catalyst Reaction Reference Results

Pt/SWNT Prenal (3-methyl-2-butenal) 171 Active and selective

Catalysis Science & Technology Minireview

Of growing interest also is the area of the designing nano-

CNT-based aerogels as supports to load catalytic matter can

Minireview Catalysis Science & Technology