COURSE: HETEROGENOUS REACTION SYSTEMS

TOPIC: HETEROGENEOUS
Ag-TiO2-SiO2 COMPOSITE MATERIALS AS NOVEL
CATALYTIC SYSTEMS FOR SELECTIVE EPOXIDATION
OF CYCLOHEXENE BY H2O2

SUBMITTED BY: PARIDHI GARG (1RV17CH024)

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 INTRODUCTION
The direct oxidation of hydrocarbons is an area with importance in academic and industrial
applications. From an industrial point of view, epoxides are widely used for the synthesis of
perfume materials, anthelmintic preparations, epoxy resins, plasticizers, drugs, sweeteners, etc.
Selective oxidation of olefins to epoxides is a central reaction in trade mark of fine chemical
synthesis. The oxidants for the epoxidation of alkenes include peracids, organic peroxides,
hydrogen peroxide, and molecular oxygen. Epoxidation reactions of alkenes generally need the
presence of a catalyst. Compared with homogeneous catalysts, heterogeneous catalysts have
many advantages such as simple separation and facile recovery of the solid catalyst from the
reaction mixture for recycling without effort. Heterogeneous catalytic systems are better than
similar homogenous catalytic systems in ways of separation of reaction products from the
catalyst. Up to now, transition metals or rare earth modified metal oxides have been studied
widely.

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Noble metals (such as Ag) have also received extensive attention due to their significant
possible applications. However, noble metal modified composite oxide on the special
interface have hardly been investigated. Thus, the epoxidation of alkene derivatives using
Ag as heterogeneous catalyst has been researched. Cyclohexene oxide and its epoxide are
important intermediate in organic process industry, and can be made by epoxidation of
cyclohexene. Hence, the catalytic epoxidation of cyclohexene remains challenging in
industry. The catalytic epoxidation using metal oxides as catalysts with high selectivity
under mild reaction conditions has become an important researching field. The
development of catalysts that may operate at room temperature and pressure for the
transformation of relatively cheap and available substrates into valuable functionalized
products has attracted the attention from both academy and industry. Recently, many
researchers have designed a series of strategies to load noble metal (Ag) for the catalytic
reaction.

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 PREPARATION OF Ag-TiO2-SiO2 COMPOSITE
All required chemicals are obtained from Nanjing Chemical Reagents and used without further
purification. Deionized water is used in all sample preparation. Titanium(IV)n-butoxide (0.7 g) and
TEOS(0.5g) are added drop wise to a TEA (6.5 g) solution. The mixture is stirred for 25 min at 298
K until a pale yellow solution is obtained, which is then transferred to a sample trough. 0.15 g of
gelatin is dissolved in 23 g of deionized water and 0.6 g of CTAB with stirring at 303 K. The sample
though is sealed and left undisturbed at 293–297 K for 48 h until a film is present on its air-water
interface. The film is transferred to a glass substrate, washed by deionized water to remove
excess CTAB, and then soaked in a silver nitrate (AgNO3) aqueous solution of 0.05 mol·L-1 for 48 h.
Finally, the soaked film is heated in a muffle at different temperature for 2 h.

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 EPOXIDATION OF CYCLOHEXENE
The catalytic performance of Ag-TS composite for the epoxidation of
cyclohexene was investigated in a 100 mL erlenmeyer flask equipped with a
stirrer, thermometer, and reflux condenser. In a typical batch experiment, to a
flask containing 80 mg of catalyst, 12 mL of chloroform and 6 mL of 30% mass
fraction H2O2 were added into the flask. Subsequently, cyclohexene (6 mL) was
added and the contents of the flask were kept in the water bath on a magnetic
hot plate for 120 min with continuous stirring at 353 K. After reaction for 2 h,
the catalyst was separated from the reaction solution by centrifugation.

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Plausible mechanism of epoxidation reaction.

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Then this separated catalyst was dried at 353 K overnight and calcined in air at 723 K for
120 min, to obtain the regenerated catalyst. The catalytic performance of the regenerated
catalyst was investigated as the same procedure as the fresh catalyst. The concentrations
in the solution was analyzed by High Performance Liquid Chromatography (HPLC) of
DIONEX U-3000 with an ultraviolet detector of VWD-3100. The chromatographic
conditions were as following: 0.02 mol·L-1 methanol aqueous solution was used as mobile
phase, the flow rate was set at 1.0 mL·min-1, the wavelength of UV irradiation was 210 nm,
the column temperature was 298 K and the injection volume was 10 μL. The epoxide yield,
the selectivity, the conversion of cyclohexene oxide and the selectivity to by-products
were evaluated 

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 MORPHOLOGY AND STRUCTURE

The XRD pattern of the four uncalcined materials are displayed in Figure 1 (a: Ag-
SiO2; b: Ag-TiO2; c: TiO2-SiO2; d: Ag-TiO2-SiO2). A predominant peak could be
observed with four samples in the 2θ range from 2° to 8°. This obvious reflection
appeared at small angle region which implied ordered structures inside of the
self-assembled inorganic-organic metal oxide. This suggests that as-prepared
TiO2-SiO2 materials are amorphous product.

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Moreover, the d value corresponded to the strongest peak meant for the
spacing between the ordered lamellas or the diameter of the ordered
mesopores inside the synthesized composite materials. The predominant
peak of TiO2-SiO2 (c) at 2θ = 3.75° give a d value of 2.39 nm. Comparison,
the diffraction peak of TiO2-SiO2 product is much weaker than that of Ag-
doped different materials and it is obvious that the 2θ angles of Ag-doped
products moved toward the smaller values, indicating the increased layer-
layer or pore-pore correlation distance with an increase of Ag content.

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LAXRD patterns of TiO2-SiO2 and Ag-TiO2-SiO2.

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The large-angle XRD patterns of the Ag-TS materials before and after calcination at
different temperature are displayed in Fig 2. Those samples obtain the same diffraction
peaks, indicates that these samples contain the same chemical composition. These
peaks observed at 2θ values of 38.3, 44.2, 64.5 and 77.4° are assigned to (111), (200),
(220) and (311) lattice planes of FCC metallic Ag (JCPDS Card NO. 04–0784),
respectively. The lattice parameter calculated from the XRD pattern is 0.4078 nm, in
agreement with the literature report. It can be seen that the diffraction peaks (d) is
very strong, indication of good crystallinity of the Ag-TS composite grain after
calcination at 723 K. It shows that calcination does not change the crystalline phase of
the Ag particles. The Ag-doped to the TiO2-SiO2 particles is characteristic crystalline
form, 2θ values of the major peaks locate in the range from 15° to 80° in accordance
with the characteristic diffraction of Ag verifying.

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HAXRD patterns of Ag-TS composite before and after calcination at
different temperature.

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Ag-TS displays a type IV adsorption- desorption
isotherms for mesoporous structure according to the
IUPAC classification.

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 FORMATION MECHANISM
The proposed formation mechanism of Ag-TS composite is illustrated in the next slide. Initially,
several CTAB molecules make a spherical micelle, the TiO2-SiO2 particles with negative charges
interact with the positively charged CTAB micelle through electrostatic interactions. This plays a
pivotal role in the subsequent assembling processes. When TiO2-SiO2 particles formed on the air-
water interfacial are soaked into the AgNO3 aqueous solution, the AgBr-TiO2-SiO2 composite are
formed due to the precipitation of AgBr at the surfaces and voids of TiO2-SiO2 particles. The
AgBr-TS particles can be prepared by a reaction of Ag ions and Br ions from CTAB. Then AgBr
decomposes into elemental Ag particles under visible light irradiation. The surfactant(CTAB) is
destructed and it has formed a stable structure of composite particles during the calcination
process. Part of the Ag particles are attached to the surface, and the rest particles remain in the
interior of the TS particles.

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Formation mechanism of the Ag-TS
composite.

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 CONCLUSION
TiO2-SiO2 particles are fabricated on air-water interface via self-assembling process and used as
the substrate of Ag particles. The Ag-TS composites are prepared by a soaking method without
using any reducing agent. Experimental results prove that Ag particles are tightly loaded on the
surface of TiO2-SiO2. XRD, SEM, EDS, BET, TEM and UV-Vis have been made use to characterize
morphologies and structures of the catalyst. The catalytic activity of Ag-TS composite after
calcination for the cyclohexene epoxidization depend on the noble metal(Ag) loaded on the
surface of TiO2-SiO2. The product calcined at 723 K has the best catalytic activity. The TiO 2-
SiO2 particles possess synergistic catalytic activity. Using it as catalyst in cyclohexene oxidization
reaction, the highest epoxide selectivity of 91.4% can be achieved. The reaction conditions, such
as reaction time and temperature have a clear influence on the catalytic performance of Ag-
TiO2-SiO2. In this experiment, the cyclohexene oxide is the main product. In addition, the activity
of the Ag-TS catalyst remains almost unchanged after three successive recycles of catalytic
reactions. This indicates that the catalyst has a better stability of activity.

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 REFERENCES
1.Bradley CA, McMurdo MJ, Don Tilley T. Selective catalytic cyclohexene oxidation using
titanium-functionalized silicone nanospheres. J. Phys. Chem. C. 2007; 111:17570–17579.
2.Yang Q, Jones W, Wells PP, Morgan D, Dong LC, Hu BS, et al. Exploring the mechanisms of
metal co-catalysts in photocatalytic reduction reactions: Is Ag a good candidate?. Appl. Catal., A.
2016; 518:213–220.
3. Wang X, Xue J, Wang X, Liu X (2017) Heterogeneous Ag-TiO2-SiO2 composite materials as novel
catalytic systems for selective epoxidation of cyclohexene by H2O2. PLoS ONE 12(5): e0176332.
https://doi.org/10.1371/journal.pone.0176332

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