Microporous and Mesoporous Materials 293 (2020) 109813

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Microporous and Mesoporous Materials

journal homepage: http://www.elsevier.com/locate/micromeso

Organic-free one-step synthesis of macro/microporous LTA zeolite and its

encapsulation of metal nanoparticles
Jian Zhang 1, Ya Wang 1, Lei Dong, Zhuwen Chen, Yanding Wang, Mei Hong *
Guangdong Provincial Key Laboratory of Nano-Micro Materials Research, School of Chemical Biology & Biotechnology, Peking University Shenzhen Graduate School
(PKUSZ), Shenzhen, 518055, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Micrometer-sized hierarchical LTA-type zeolite crystals with uniform embedded macropores were synthesized
Mesoporous silica microsphere via steam-assisted conversion (SAC) of spherical mesoporous silica particles (MSPs) impregnated with alkaline
Zeolite aluminate. The one-pot synthesis was achieved by direct transformation without the need of organic structure
LTA
directing agents or pre-formed seeds. The obtained cubic hierarchical NaA zeolite materials were 2–5 μm in size
Steam-assisted conversion
Nanoreactor
which possessed a core-shell structure with a microporous wall in the shell and multi-hollow macropores about
400 nm in the core. Time-series studies revealed the in situ dissolution–crystallization formation mechanism, in
which the mesoporous silica particles functioned as silica source as well as “space-filling” template. When the
starting MSPs were pre-loaded with metal precursors, multi-hollow zeolite nanoreactor crystals with encapsu­
lated metals were successfully synthesized by this strategy. The present study provides an organic-free way to
fabricate hierarchical aluminosilicate zeolites with embedded macropore system.

1. Introduction synthetic strategies to build up hierarchical zeolites, typically with the

aid of hard- or soft-templates [6]. These secondary diffusion pathways
Microporous zeolites are widely used as industrial adsorbents, ion- are usually mesopores as can be found in several reviews [7,8]. A few
exchangers, and catalysts due to their excellent shape selectivity, studies have investigated the preparation of macroporous zeolites [9].
tunable chemical compositions, and high thermal/hydrothermal sta­ The macroporous zeolites could be arranged as mechanically stable
bilities [1], while their new applications as in chemical sensing and monolith [10–13] utilizing the macropores to favor mass transfer and
biomedicines are emerging [2]. Conventional bulk zeolites with sole reduce transport limitations [14]. They exhibited advantages in various
microporous framework have their intrinsic weaknesses in terms of applications including membrane bioreactors [15], improved catalysts
guest molecule diffusion, leading to reduced access to active sites and involving bulky reactants [16–19], and controlled release [20].
severe coke formation when used in high temperature fast reactions [3]. The syntheses of macroporous zeolites have been investigated mostly
Nano-sized zeolites, or nano-zeolites with decreased crystal dimensions, with morphologically predefined templates. One strategy is to employ
although shortens the diffusion pathways of the reactants/products, inert hard templates using polymers including polystyrene (PS) spheres
suffer from low synthesis yield and aggregation tendency during [21–24], latex beads [10], polyurethane foams [11], biopolymeric ma­
handling [4]. Recently, nano-architecture design of intrinsically micro­ trix such as starch gels [12,25,26], bacteria [27], and inorganic CaCO3
porous zeolites has received considerable attention in order to generate [20]. The zeolite growth on these templates usually employs
hierarchically organized pore system for more efficient mass transfer. A layer-by-layer assembly technique [28] by alternatively depositing
great number of strategies have been developed to create hierarchical oppositely charged zeolite nanoparticles and polyelectrolytes onto the
zeolites with secondary diffusion pathway, including “top down” and templates that do not alter during zeolite crystallization and are subse­
“bottom up” approaches. The top down strategy involves post-synthetic quently removed through calcination in order to release the macropores.
treatment of the microporous zeolites, sometimes in the presence of This inert hard templating strategy can be applied to any zeolite struc­
structure directing agent [5]. The bottom up approach involves ture if compatibility issue of the support with the synthesis medium can

* Corresponding author.
E-mail address: hongmei@pkusz.edu.cn (M. Hong).
1
These authors contributed equally.

https://doi.org/10.1016/j.micromeso.2019.109813
Received 29 April 2019; Received in revised form 5 October 2019; Accepted 17 October 2019
Available online 20 October 2019
1387-1811/© 2019 Elsevier Inc. All rights reserved.
J. Zhang et al. Microporous and Mesoporous Materials 293 (2020) 109813

be solved and the resulting zeolite crystals are small enough to cover reported procedure [30] in a three-neck flask at room temperature with
uniformly the templating objects [29]. Alternatively, sacrificing tem­ mechanical stirring. In a typical procedure, 0.6 g CTAB was dissolved in
plates that also take part into the zeolitization process by providing a mixed solvent containing 83 ml distilled water and 288 ml ethanol and
framework species besides working as a temporary template to induce was vigorously stirred for 10 min. Then, 14.5 ml ammonium solution
macroporosity are attractive. These sacrificing hard templates are usu­ (25%) was added, stirred for 1 h, followed by addition of 2 mL TEOS to
ally silicon precursors such as mesoporous silica particles (MSPs) [15,19, form a clear solution. This solution was further stirred for 2 h, and the
30], or silica coated on pre-defined support surface [31]. Schwieger and obtained white precipitate was separated by refrigerated centrifugation
coworkers developed a simple steam-assisted crystallization (SAC) and dried at 60 � C overnight. Finally, CTAB was removed from the
approach using tetrapropyl ammonium hydroxide (TPAOH) impreg­ as-synthesized MSP via calcination at 600 � C in air for 10 h.
nated MSPs and successfully synthesized micro/macroporous silicalite-1
zeolite crystals with embedded macropores [30]. Zhang et al. extended 2.3. Synthesis of metal-loaded mesoporous silica microspheres
this approach by starting with aluminum and alkali aqueous solution
impregnated MSPs, which afforded hierarchically macro/microporous Preparation of gold-loaded mesoporous silica microspheres (Au-
ZSM-5 single crystals [19,32]. Although these studies have been suc­ MSPs): The mesoporous silica microspheres were first functionalized
cessfully applied to the fabrication of macroporous zeolites, the frame­ with amino group before gold loading according to literature procedures
work type has been limited to MFI zeolites under the assistance of [46] with slight modification. Into 50 mL toluene, 1 g MSP was first
organic structure-directing agent of TPAþ. Herein, we report the added and stirred at room temperature, followed by slow addition of
organic-free synthesis of macroporous LTA-type (MaLTA) zeolites with 10 mL (3-aminopropyl)triethoxysilane (APTES). The suspension was
high aluminum content, classical cubic morphology, and embedded further stirred for 1 h before heating to reflux for 10 h. The silylated MSP
intracrystalline macropores by simply one-pot transformation of MSP was washed via repeated centrifugation, decanting, and ultrasonic
and aqueous alkaline aluminate for SAC. dispersion in ethanol for three times, followed by vacuum drying at
Recently, great efforts have been devoted to the controllable syn­ 60 � C for 10 h. Then the amino functionalized MSP were mixed with
thesis of uniform nanometals in zeolite system. Metals encapsulated in HAuCl4�4H2O at a mass ratio of 5:1, stirred at room temperature for
zeolite frameworks can strictly control the nanoparticle size as well as 12 h, centrifuged, and redispersed in deionized water. Hydrochloric acid
limit metal sintering at high temperature [33]. Confinement of noble was added until pH < 2, and the dispersion was continuously stirred for
nanometals in a zeolite matrix shows unique molecular-scale effects 30 min before dropwise addition of 50 mmol/L sodium borohydride
enabling advantageous nanoreactors with spatially confined catalysis solution. The metal reduction reaction took place under continuous
[34]. Compared with post-synthetic impregnation method, direct crys­ stirring for 10 h, followed by centrifugation and drying under vacuum to
tallization of zeolites in the presence of dispersed metal precursors can afford gold-loaded mesoporous silica microspheres.
realize more homogenous distribution of metals in the zeolite crystals Preparation of platinum-loaded mesoporous silica microspheres (Pt-
which are catalytically more active [35]. By fast steam assisted con­ MSPs): The Pt-MSPs were prepared following literature procedures [47].
version of tetrapropylammonium hydroxide impregnated mother sup­ 0.5 g of mesoporous silica microspheres were immersed in an impreg­
ports of Ti-MCM-41 and Ti-SBA-15, Kang et al. fabricated hierarchical nation solution of 0.05 mol/L H2PtCl6�6H2O for 8 h. Thereafter, the
titanium-containing mesoporous materials with MFI crystalline struc­ impregnated microspheres were dried at 120 � C for 12 h, and then
ture [36]. The LTA-type zeolites are important industrial adsorbents and calcined at 550 � C for 3 h in a muffle furnace to yield platinum-loaded
ion exchangers [37]. They are also ideal model systems for investigating mesoporous silica microspheres.
aluminosilicate zeolite nucleation and growth mechanism [38,39].
Various metals have been encapsulated into LTA zeolites, including Cu, 2.4. Synthesis of macroporous LTA zeolite crystals and metal@MaLTA
Rh, Pd, Ag, Ir, Pt, Au [40–44], and bimetallic clusters such as AuPd, heterostructures
AuPt, and PdPt [45], thanks to the small channel apertures with pore
size of 0.41 nm and abundant surface hydroxyls ready to accommodate Mesoporous silica microspheres were used as a sacrificial template to
alkoxylsilanes in LTA framework. The LTA encapsulated metals participate in the synthesis of macroporous LTA zeolites in a SAC setting.
exhibited enhanced catalytic activities in chemoselective hydro-/­ In a typical synthesis procedure, 100 mg of MSP were sonicated in 2 ml
dehydrogenation [40–42,45] and selective catalytic reduction of NOx deionized water, followed by the addition of 66 mg NaOH and 136 mg
with NH3 [43], as well as remarkable luminescence properties [44]. In NaAlO2, resulting in a mixture with a molar composition of 1Al2O3:2­
this study, we demonstrated that the inherent mesoporosity in MSP SiO2:2Na2O:135H2O. The mixture was placed in a Teflon holder and
allowed for easy metal encapsulation during zeolite crystallization, and allowed to dry at room temperature for 12 h. The Teflon holder was then
heterostructures of Au or Pt incorporated in MaLTA have been obtained, placed in an autoclave containing 15 ml of water at the bottom and
which holds potential as catalytically active nanoreactors. steam-assisted crystallization was conducted at 110 � C for 12 h. After
crystallization, the autoclave was cooled to room temperature in cold
2. Experimental section water. The resulting powder collected with a refrigerated centrifuge was
washed with deionized water until pH of the supernatant was close to 7,
2.1. Chemicals and reagents and dried at 60 � C for more than 12 h.
The metal@MaLTA heterostructures were prepared with the same
All reagents were of analytical grade and used as purchased without procedure except that metal-loaded MSP samples were utilized instead.
further purification. The inorganic salts of sodium hydroxide and so­ The subsequent SAC of Au-MSPs and Pt-MSPs afforded metal@MaLTA
dium aluminate were purchased from Adamas-beta. Surfactant of crystals, named as Au-MaLTA and Pt-MaLTA.
cetyltrimethylammonium bromide (CTAB), metal precursors of
HAuCl4�4H2O and H2PtCl6�6H2O, silica precursor of tetraethyl ortho­ 2.5. Characterization
silicate (TEOS), silanization agent of (3-aminopropyl)triethoxysilane
(APTES), and reducing agent of sodium borohydride were obtained from Powder X-ray diffraction (XRD) patterns of zeolite was recorded
Aladdin. using a Rigaku D/Max-2200 PC diffractometer in the diffraction angle
range 2θ ¼ 4–50� with Cu Ka radiation (λ ¼ 1.5418 Å) at 40 KV, 40 mA.
2.2. Synthesis of mesoporous silica microspheres Scanning electron microscope (SEM) was performed on a JEOL JSM-
7800F electron microscope operated at 8.0 KV. The transmission elec­
The preparation of MSP was carried out according to a literature tron microscopy (TEM) and high-angle annular dark field-scanning

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J. Zhang et al. Microporous and Mesoporous Materials 293 (2020) 109813

transmission electron microscopy (HAADF-STEM) were performed on a

FEI Tecnai G2 F30 field emission source transmission electron micro­
scope operated at 300 kV. To reveal the inner structure, zeolite samples
were embedded in a spur epoxy resin and ultramicrotomed to a thick­
ness of 80 nm for cross-sectional TEM measurement. Elemental analysis
was conducted by inductively coupled plasma-atomic emission spec­
troscopy (ICP-AES), based on which Si/Al ratio of as-synthesized sam­
ples were calculated. Metal content of the as-synthesized samples were
also measured by ICP-AES (JY 2000-2). Centrifugation of suspension
samples was conducted by a refrigerated centrifuge (Thermo Scientific -
Fiberlite F21s-8x50y). Electron tomography (ET, 3D-TEM) was per­
formed in bright-field mode with a FEI Tecnai G2 F30 electron micro­
scope. The microscope was equipped with a TWIN objective lens, a LaB6
electron source and was operated at 300 kV. TEM grids were prepared Fig. 1. (a) SEM image of the external surface of MSP, inset is the corresponding
by dropwise addition of homogenous suspension of zeolite in ethanol, particle-size distribution; (b) TEM image of one ultramicrotomed slice of MSP.
followed by drying in air at 60 � C. These grids were initially labelled
with 5 nm gold particles by applying a droplet of colloidal gold sus­ The external appearance of the MaLTA zeolite synthesized using
pension on a carbon-coated Quantifoil R2/1 copper grid with parallel MSPs as the sacrificial template was cubic with particle sizes between 2
bars in order to provide markers for alignment of tilt images. Tilt series and 5 μm (Fig. 2a). The cubic outline was almost identical to that of
of images were acquired using Xplore3D software over an angular range conventional A-type zeolite previously synthesized using organic-free
of �70� with a tilt increment of 1� or 5� . Images were recorded on a 2048 hydrothermal synthesis without secondary porosity (Fig. S2) [39,49].
x 2048 pixel TVIPS CCD camera. Alignment of the acquired tilt images However, when the MaLTA zeolite particles were grounded and crushed,
was performed using the inspect3D software and facilitated by tracking core-shell structure was unraveled. The interior of the zeolite crystals
the gold markers. 3D reconstruction of the aligned images was done by had a large amount of macropore void structure (Fig. 2b). These voids
filtered back projection using the same software. 3D visualization and were either interconnected channels or isolated cavities. The average
analysis were performed by Amira software to better explore the pore macropore size was about 450 nm, which is slightly smaller than the
channel structure. Nitrogen Gas adsorption-desorption isotherms at particle size of initial MSP (Fig. 1), similar to the previous micro/­
196 � C were obtained on a Micromeritics Tristar II 3020 v1.03 macroporous MFI-type zeolite crystals prepared from steam-assisted
analyzer. Argon adsorption-desorption isotherms were measured at crystallization of MSP in the presence of organic structure directing
186 � C and carbon dioxide adsorption were conducted at 0 � C. For all agent of TPAOH [30], which also produced macroporous void space
these gas sorption experiments, the powder samples were degassed at with pore size slightly smaller than the particle size of the startinxg MSP.
200 � C in vacuo for at least 6 h before measurements. The Brunauer- The microspherical MSP played dual functions: zeolite growth nutrients
Emmett-Teller (BET) surface areas were calculated from the adsorp­ of silicon and hard templates leading to macropores. The clearly
tion data from 0.01 < P/P0 < 0.20. The mesopore size distributions were discernible lattice fringes in the form of parallel (200) planes in the TEM
determined using the Barrett-Joyner-Halenda (BJH) model. (Fig. 2d) of the MaLTA zeolite confirmed the superb crystal periodicity,
demonstrating that the macroprous zeolite had a high degree of crys­
3. Results and discussion tallinity. The Si/Al ratio of the bulk MaLTA was 1 as measured by
ICP-AES analysis.
3.1. Structural characteristics of macroporous LTA zeolites In order to obtain the overall structure of the zeolite and the three-
dimensional visualization of the internal macropores, an electron to­
The synthesis process for MaLTA is shown in Scheme 1, which in­ mography scan (3D-TEM) was performed on a partially fractured MaLTA
volves microspherical mesoporous silica particle (MSP) preparation, zeolite particle (Fig. 3, video 1-2 in Supporting Information), unravel­
impregnation with alkaline and aluminum source, and steam-assisted ling more comprehensive view of the core-shell zeolite. The macropores
transformation. When the as-synthesized MSP samples were loaded in the core induced by MSPs are concentrated in the center of the zeolite.
with metal sources for nanoreactor preparation, metal@MaLTA samples They remain either as independently existing cavities or interconnected
were obtained. The starting MSP were monodisperse exhibiting uniform channels in the cross-sectional planes.
sizes of 550 � 100 nm with smooth surfaces (Fig. 1a) and clearly Supplementary video related to this article can be found at doi:10.10
observable mesopores (Fig. 1b), which were the sole silicon source for 16/j.micromeso.2019.109813
the synthesis of macroporous LTA zeolites. The N2 physisorption
isotherm (Fig. S1a) shows a type IV isotherm that is characteristic of 3.2. Formation mechanisms of core-shell macroporous LTA zeolites
mesoporous materials [48]. The mesopore size was 2.88 nm (Fig. S1b).
To gain insights into the crystallization process which transformed

Scheme 1. Detailed fabrication process of MaLTA zeolites based on steam-assisted transformation of MSP.

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J. Zhang et al. Microporous and Mesoporous Materials 293 (2020) 109813

Fig. 4. SEM images of MaLTA samples at different SAC stage of (a) 3 h, the
inset shows the cross-sectional TEM image, (b) 6 h, (c) 9 h, the inset shows the
SEM image of one broken crystal, and (d) 12 h.

silica adhered to or remained embedded in the bulk LTA crystals. After

9 h of reaction (Fig. 4c), the MSP particles almost disappeared, and the
Fig. 2. (a) SEM image of the external appearance of intact MaLTA crystals SEM images revealed mostly cubic LTA crystals with structural macro­
showing cubic outline; (b) SEM image of one broken MaLTA crystal showing pores both on the crystal surface and in the interior, as clearly shown in
embedded macropores; (c) TEM image of an 80-nm ultramicrotomed slice; the the inset SEM image of Fig. 4c. With the increase of SAC time to 12 h, the
breakage is believed to result from the ultramicrotomy action which indicates MSPs particles completely disappeared, and the dented crystals became
high mechanical strength of the zeolite crystal. (d) High-resolution TEM of the
smooth with perfected cubic outline, thus the zeolite precursors more
marked region in (c) showing uniformly oriented lattice fringes with a spacing
likely migrated from the pore to the external surface during zeolite
of 1.23 nm expected for (200) facets of LTA-type zeolites.
crystallization for the ease of transport [50].
These dynamic observations indicate that MSPs gradually dissolved
as synthesis time increased which not only provided nutrients as silicon
source for zeolite formation, but also served as pore-filling templates for
macropore formation. The synthesis mechanism of MaLTA is proposed
as shown in Fig. 5. Initially, the MSPs were impregnated with the
alkaline solution containing aluminum source (Fig. 5b). When these
impregnated MSPs were heated to the crystallization temperature under
SAC conditions, the penetrated alkaline solution began to dissolve the
amorphous MSPs, enlarging their internal mespores and slightly
shrinking the microsphere sizes (Fig. 5c). At this point, the aqueous
concentration of Si around the microspheres increased, which changed
the local microenvironment resulting in the formation of zeolite crystals
around the microspheres (Fig. 5d). The continuous dissolution and
crystallization process caused crystals to grow in the interparticle region
Fig. 3. (a) TEM image of one broken MaLTA; and (b) the corresponding 3D- of MSPs, producing zeolite crystals embedded with MSP residues
TEM image.
(Fig. 5e) as well as vacancies left by the dissolved MSPs. The steaming
condition initiated the crystallization process between the rich
aqueous alkaline aluminate impregnated MSPs into MaLTAs, time- aluminum source impregnated in the mesopores and the silicon source
resolved crystallization was studied, which revealed the dynamics of of starting MSPs, triggered Si-O-Si bond breaking of the reactant silica
in situ dissolution-crystallization in an organic-free approach. Fig. 4 microspheres and formation of the periodical Al-O-Si bonds, leading to
shows the SEM images of the product collected at different crystalliza­ formation of NaA zeolite with LTA topology and Si/Al ratio of 1. In the
tion period. The initial product obtained at 3 h was still amorphous but final stage of SAC, zeolite crystal surface was healed due to the easy
with visible dissolution of MSPs as can be seen from the SEM and inset transport of nutrients needed for crystal surface defect patching by the
TEM image in Fig. 4a exhibiting enlarged internal mesopores. The accelerated dissolution of the remaining MSPs through in-situ generated
dissolution occured in both the exterior and interior of MSPs, indicating zeolite seeds. The only slightly smaller macropores size of ~450 nm
penetration of the liquid alkaline solution through the mesopores into compared to the initial MSP size of 550 � 100 nm demonstrated the
the interior of solid MSPs, probably started during the intial static scaffold templating role of the silica microspheres during zeolite crys­
mixing period and continued during the SAC process. With the liquid tallization. Similar to previous studies that utilized MSP particles to
infusion into the voids of solid, MSP underwent partial dissolution into synthesize macroporous ZSM-5 zeolites [19] involving outward disso­
the reaction solution, leaching Si content and simultaneously forming lution of the aluminosilicate precursor and concurrent recrystallization
LTA zeolite. So that when the reaction proceeded to 6 h (Fig. 4b), LTA of Si and Al species under the guidance of the TPA cations, the current
crystals were generated as continuous phase between MSPs. There were observations suggest that the MSPs were gradually dissolved with the
many defects as dented vacancies dispersed on the crystal surface. Some increasing steaming time as a way to supply the silicon sources for the
of the MSPs did not dissolve completely and these residual amorphous formation of the aluminosilicate zeolite. The dissolution of MSPs most

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J. Zhang et al. Microporous and Mesoporous Materials 293 (2020) 109813

Fig. 5. Schematic representation of MaLTA formation process: (a) MSP structure after calcination; (b) impregnated MSPs; (c) Initial MSP dissolution; (d) Zeolite
formation around MSPs; (e) Zeolite crystals with embedded MSPs; (f) Final MaLTA zeolite crystals.

likely start at the surface of these MSPs where the formation of zeolite impregnation method was used for platinum loading. Fig. 6 compares
matrix took place. The bulk MSP microspheres probably restricted ex­ the XRD patterns of mesoporous silica microspheres (MSPs), gold-loaded
change of external nutrient solutions and thus conversion to LTA mainly mesoporous silica microspheres (Au-MSPs) and platinum-loaded meso­
occurred at their exterior. The continued consumption of the MSPs and porous silica microspheres (Pt-MSPs). All showed a characteristic broad
the transformation to zeolite led to embedded macropores in the final diffraction peak at 22� attributed the amorphous structure of silica. Four
product, leaving macropores in the synthesized zeolite crystals (Fig. 5f). distinct peaks at 2θ ¼ 38.0� , 44.1� , 64.4� , 77.5� and 81.6� in the XRD
As the size of MSP is adjustable by altering synthesis procedures such the patterns of Au-MSPs belong to diffraction from (111), (200), (220),
surfactant amount [51,52], it is therefore possible to control the internal (311), and (222) facets of the typical face-centered cubic (fcc) phase of
macropore diameter in zeolites by adjusting the particle size of the Au crystals (JCPDS no. 04–0784) [57], indicating that Au crystals have
MSPs. been successfully loaded in MSPs. Similarly, XRD pattern of Pt-MSPs
An interesting feature of this synthesis process is the use of only MSPs exhibited characteristic peaks at 2θ ¼ 40.0� , 46.2� and 67.0� , attrib­
as a quasi “space-occupier” to form well-shaped large macroporous low- uted to the fcc platinum (111), (200) and (220) crystal faces (JCPDS no.
silica zeolite crystals without the need to coat preformed seeds or using 05–0681) [58], confirming platinum incorporation in the MSPs. The
organic structure directing agents (OSDA). The dissolution of MSP and peak intensity is relatively low probably due to the low loading.
crystallization of aluminosilicate zeolites occurred synergistically, After ultra-microtomy of metal loaded MSPs and the transformed
which are probably boosted by the generated steam in the autoclave metal@MaLTA zeolites, they were subjected to TEM and HAADF-STEM
providing humid atmosphere and thus influencing the dissolution and imaging (Fig. 7). Due to the strong coordination ability of alkylamino
crystallization of the precursors [53]. In previous studies, the trans­ group, the added gold precursors could be covalently bonded on MSP,
formation of MSPs only yielded MFI crystals with the aid of zeolite seeds and upon reduction, Au nanoparticles with size of 10–20 nm were
[13] or OSDA of tetrapropylammonium salts [19,30,32,54]. homogenously distributed both in the interior and exterior. The Pt
nanoparticles incorporated in the MSPs were much smaller, < 5 nm in

3.3. Fabrication of metal@MaLTA heterostructures

The regular mesopores in MSP templates and the organic-free one-

pot transformation to core-shell multi-hollow zeolites facilitate easy
loading of guest species, such as metal precursors. The pre-incorporated
metal precursors in the mesopores of the MSP can be entrapped inside
the generated hollow capsules along with digestion of the MSP templates
[55]. Zeolite molecular sieve, as the form of micro reactor, has its own
acid catalytic capacity not always meeting the requirements of diverse
reactions, so the spatially resolved loading of other catalytic components
in zeolite made them a potential nanoreactor [31]. The macropore
cavity induced by MSPs enabled encapsulation of the metal nano­
particles and the versatility of MaLTA zeolite imparted additional
properties due to the hybrid nature of the resulting nanocomposites
[56].
In order to find out whether the steam-assisted zeolitization process
are generally applicable to different metal-loaded silica microspheres,
two different metals and two different metal-loading methods were Fig. 6. XRD patterns of MSPs, Au-MSPs and Pt-MSPs. The (hkl) of the metal
tested. Capping agent of APTES was employed for gold loading and wet crystal facets was indexed to each corresponding peak.

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J. Zhang et al. Microporous and Mesoporous Materials 293 (2020) 109813

Fig. 7. SEM, cross-sectional TEM, and HAADF-STEM images of MSPs (first row), metal-MSPs (second row) and transformed metal-MaLTA (third row) samples, scale
bar represents 200 nm. Insets in the SEM images are pictures of the samples showing the visual appearance.

size, and more uniformly distributed in the interior of the microspheres,

indicating that the Pt nanoparticles were mostly loaded into the chan­
nels of the mesoporous silica. After SAC, the metal NPs were well
encapsulated in the zeolite interior. The Au nanoparticles can be directly
observed to be homogeneously dispersed inside the zeolite crystals,
which size did not change much by SAC. The Pt distribution shows
certain degree of heterogeneity. While the Pt size was still ultrasmall less
than 5 nm, they exhibited slight aggregation probably due to the exis­
tence of macropores which allowed mobility of the tiny Pt nanoparticles.
This is consistent to the general findings that capping agent assisted
metal loading exhibited advantages with regard to homogeneity of
metals and resistance to sintering [34].
The metal incorporation did not affect SAC transformation of MSPs
into zeolite LTA, as confirmed in XRD patterns of all three samples
(Fig. 8), showing sharp peaks indicating high crystallinity. The metal
nanoparticles incorporation changed little on surface area and pore
diameter of the MaLTA zeolites (Fig. S3). Pure LTA phase can be iden­ Fig. 8. Comparative XRD patterns of MaLTA, Au-MaLTA, and Pt-
tified, indicating the complete reaction between Si and Al precursors of MaLTA samples.
MSP and NaAlO2. Therefore, the steam-assisted crystallization success­
fully transformed both metal-loaded silica microspheres impregnated
yielding metal-MaLTA heterostructures, which have great potentials as
with alkaline aluminate into metal-encapsulated macroporous LTA ze­
nanoreactors for heterogeneous catalysis and molecular sieving. The
olites regardless of the metal incorporation method. While the Au-MLTA
present study provides a new strategy to synthesize macroporous func­
XRD showed characteristic peaks of Au nanoparticles at 38� , peaks
tional zeolites with varied composition and controlled architecture.
belonging to Pt were not discernible probably due to the relatively small
amount of Pt loading. The metal contents of Au and Pt in the trans­
Declaration of competing interest
formed metal loading macroporous LTA zeolite crystals were measured
by ICP-AES analysis, which were 900 and 5.74 ppm in Au-MaLTA and
The authors declare that they have no known competing financial
Pt-LTA respectively based on weight percent.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
4. Conclusions
Acknowledgements
Core-shell LTA zeolites with embedded macropores have been ob­
tained through the one-pot organic-free steam-assisted crystallization of
We are grateful to the financial support from the National Natural
amorphous mesoporous silica microspheres impregnated with alkaline
Science Foundation of China (21671010), the Guangdong Science and
aluminate. The sacrificial MSPs provided nutrient in the framework
Technology Program (2017B030314002), the Programs of Science and
construction and acted as hard template for macropore formation due to
Technology of Shenzhen (JCYJ 20170818085754055,
the restricted inward diffusion in the synthesis condition. By analyzing
GJHZ20180928162402322) and Postdoctoral Science Foundation of
time-series samples at different crystallization stages, the crystallization
China (2018M641092).
mechanism was elucidated. The crystallization process started with the
dissolution of the MSPs. Along with this dissolution and mass exchange,
Appendix A. Supplementary data
crystals began to form in the intraparticle domains of MSPs, which after
continued dissolution and defect patching, afforded high-crystallinity,
Supplementary data to this article can be found online at https://doi.
low-silica zeolite with internal macropore structure. Through functio­
org/10.1016/j.micromeso.2019.109813.
nization of MSPs with metal precursors, the metal particles can be easily
transferred and encapsulated into the interior of the zeolite, efficiently

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J. Zhang et al. Microporous and Mesoporous Materials 293 (2020) 109813

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