Amino Acid-Assisted Construction of Single-Crystalline Hierarchical

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Amino Acid-Assisted Construction of Single-Crystalline Hierarchical Nanozeolites via Oriented-Aggregation and Intraparticle Ripening Qiang Zhang, Alvaro Mayoral, Osamu Terasaki, Qing Zhang, Bing Ma, Chen Zhao, Guoju Yang, and Jihong Yu J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 22 Feb 2019 Downloaded from http://pubs.acs.org on February 22, 2019

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Journal of the American Chemical Society

Amino Acid-Assisted Construction of Single-Crystalline Hierarchical Nanozeolites via Oriented-Aggregation and Intraparticle Ripening Qiang Zhang,† Alvaro Mayoral,§ Osamu Terasaki,§ Qing Zhang,§ Bing Ma,# Chen Zhao,# Guoju Yang,† Jihong Yu*,†,‡ †State

Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China ‡International §School

Center of Future Science, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China

of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, P. R. China

#Shanghai

Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University, North Zhongshan Rd. 3663, Shanghai 200062, P. R. China Supporting Information Placeholder ABSTRACT: Hierarchical nanozeolites are highly desired for

heavy oil conversion because of their fast mass transfer, good site accessibility, and short diffusion length compared with their conventional counterparts. Here, we provide a facile amino acid-assisted strategy to synthesize hierarchical ZSM-5 (MFI) zeolite nanocrystals by two-step crystallization in a concentrated gel system. Strikingly, each virus-like zeolite nanoparticle with abundant interconnected intracrystalline mesopores is a high-quality single crystal that is defect-free as confirmed by electron diffraction and NMR analysis. By utilizing advanced electron microscopy techniques, we have studied the evolution process of single-crystalline hierarchical ZSM-5 nanocrystals that involves oriented aggregation of protozeolitic nanoparticles formed at low temperature followed by intraparticle ripening at high temperature. The as-prepared hierarchical Ni@ZSM-5 catalysts exhibit superior catalytic performance in hydrodeoxygenation of stearic acid and palm oil.

Zeolites with uniform micropores, tunable acidities, and high thermal/hydrothermal stability are important shapeselective catalysts in petrochemical industry.1 Particularly, ZSM-5 (MFI-type) zeolites are extensively used in various important catalytic processes.2 However, the sole microporosity of conventional zeolites restricts the catalytic performance when bulky reactants/products are involved.3 Integrating mesopores into zeolite structures has proven to be an effective strategy to overcome the accessibility, diffusion, and mass transportation limitations, thus improving the catalysis efficiency.4 So far, several approaches including destructive approaches (e.g., dealumination and desilication) and constructive methods (e.g., using hard or soft templates as mesoporogens) have been developed toward the synthesis of hierarchical zeolites.5 Notably, Ryoo’s group firstly succeeded in synthesizing hexagonally ordered mesoporous MFI zeolites by using gemini-type dual-porogenic surfactants;6

Che’s group also synthesized highly ordered mesostructured MFI zeolites using designed templates.7 However, these ordered mesoporous MFI zeolites are polycrystalline for the whole particles that are vulnerable to hydrothermal treatment. Therefore, fabrication of single-crystalline hierarchical zeolites with superior hydrothermal stability is of great importance. To this end, Xiao’s group successfully synthesized single-crystalline zeolite by using mesoporogendirected approach.8 It is noted that the current synthesis approaches for hierarchical zeolites with disordered or ordered mesopores generally cause a high level of framework defects. Thus, the synthesis of single-crystalline and defectfree hierarchical nanozeolites is highly desired for practical industrial catalytic applications. Herein, we demonstrated a novel kinetic-modulated crystallization approach for constructing single-crystalline and defect-free hierarchical ZSM-5 nanocrystals. This was based on our previously developed strategy by synergistically using L-lysine-assisted two-step crystallization in a concentrated gel system.9 Differently from our previous approach in which a small amount of L-lysine solely acted as crystal growth inhibitor to produce nanosized zeolite single crystals, in this work, excess L-lysine was added to induce oriented aggregation of protozeolitic nanoparticles formed at low temperature in a non-compact manner. Subsequently, intraparticle ripening at high temperature led to the formation of abundant interconnected mesopores. Via this strategy, we successfully synthesized single-crystalline and defect-free hierarchical ZSM-5 nanocrystals with high crystallinity, good monodispersity, high product yield, high hydrothermal stability, and superior catalytic properties. Typically, a mixture with molar composition of 1.0 SiO2: 0.003 Al2O3: 0.015 Na2O: 0.45 TPAOH: x L-lysine: 9 H2O (x=0, 0.1, and 0.4;) was first crystallized at 90°C for 2 days, then heated at 170°C for 1 day. Table S1 lists the synthetic conditions. All the samples are MFI-type zeolites as confirmed by powder X-ray diffraction (XRD) analysis (Figures S1 and S2).

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(denoted as 1 in Figure 2a) shows MFI structure along b-axis (Figures 2c and 2d). Furthermore, all “T” atomic columns forming the 5-ring, 6-ring, and 10-ring channels can be clearly identified. The integrity of the hierarchical zeolite structure is also confirmed by the Cs-corrected STEM-ADF and STEM-Annular Bright Field (ABF) images (Figures S13cf).

Figure 1 (a) Low-magnification low-voltage high-resolution scanning electron microscopy (LV-HR-SEM) image, (b) lowmagnification transmission electron microscopy (TEM) image, (c) high-magnification LV-HR-SEM image, and (d) high-magnification TEM image of Z-L0.4C-90(2d)/170(24h) The amount of L-Lysine greatly affects the crystal size and formation of mesopores. As can be seen from the SEM and TEM images in Figures S3 and S4, Z-L0C-90(2d)/170(24h) synthesized without L-Lysine shows a regular morphology with crystal size of ca. 183 nm and no mesopores are observed. Z-L0.1C-90(2d)/170(24h) synthesized with a small amount of L-Lysine possesses nanosize (ca. 71 nm) and small isolated mesopores (ca. 2 nm); Z-L0.4C-90(2d)/170(24h) synthesized with excess L-Lysine consists of uniform viruslike nanoparticles with size of ca. 155 nm (Figures 1a, 1b, and S5), which are featured by abundant interconnected mesopores with sizes of ca. 40 nm (Figures 1c, 1d, and S6). N2 adsorption/desorption analysis reveals that Z-L0.4C90(2d)/170(24h) possesses higher micropority than Z-L0.1C90(2d)/170(1d) and Z-L0C-90(2d)/170(24h) (Figure S7 and Table S2). This indicates that the increase of the amount of Llysine favors the increase of zeolite crystallinity. Note that the L-lysine/Si ratio of 0.4 is the optimized condition affording the hierarchical zeolites. Increasing the L-lysine/Si ratio to 0.6 or 0.9 results in the formation of micron-sized MFI zeolites without mesopores (Figures S8 and S9). Notably, hierarchical zeolites can be only obtained by simultaneously combining the three approaches, i.e., two-step crystallization, addition of excess L-lysine, and concentrated system (Figures S10-12 and Table S2). Figure 2a depicts the Cs-corrected scanning transmission electron microscopy-Annular Dark Field (STEM-ADF) image of a typical Z-L0.4C-90(2d)/170(24h) nanocrystal on the [010] orientation as confirmed by the FFT diffractogram (Figure 2b), which can be indexed assuming Pnma space group symmetry based on MFI structure. The images show the coexistence of both micropores and intracrystalline mesopores with maximum diameter of ca. 40 nm (Figures 2a and S13a). Different ED patterns of individual particles corroborate the single-crystalline nature of the sample. Figure S13b shows the data obtained from the [100] orientation that confirm this fact, indicating the 3D continuous zeolite framework. The high-resolution atomic visualization of the framework at the crystal periphery

We further investigated the intermediates of Z-L0.4C90(2d)/170(24h) at different periods. The LV-HR-SEM image shows that Z-L0.4C-90°C(1d) is comprised of ultrasmall nanoparticles with diameters of ca. 8-20 nm (Figure S14a). XRD pattern shows that these nanoparticles are predominantly amorphous (Figure S15), but N2 adsorption/desorption reveals that they already possess microporous feature with micropore volume of 0.08 cm3g-1 (Table S3). Such nanoparticles could be claimed as protozeolite possessing only a short-range atomic order characteristic of a crystalline framework.10 By prolonging the crystallization time to 1.08d, 1.5, and 2 days at 90°C, the protozeolitic nanoparticles aggregated, resulting in the formation of integrated nanocrystals with increasing size and crystallinity (Figures S14b-d and S15). Notice that the size of individual protozeolites in the nanocrystals remained unchanged at different periods. When the crystallization temperature was raised to 170°C, the integrated zeolite crystals remained unchanged in size at different time, while the protozeolitic primary nanoparticles coalesced into larger ones (ca. 60 nm), resulting in the appearance of interconnected mesopores in the integrated nanocrystals (Figures S14e-g). Figure S16 shows the TEM images of intermediates at different periods, displaying the evolution process of intracrystalline mesopores varying from initially isolated ones to final interconnected ones. The intermediates possess good crystallinity and increased micropore volume (0.08-0.13 cm3/g) (Table S3).

Figure 2 (a) Cs-corrected STEM-ADF image of Z-L0.4C90(2d)/170(24h), (b) FFT diffractogram from the region 1 in (a), atomic-resolution ADF image (c) and (d) ABF image of region 1 Figure 3a shows that Z-L0.4C-90°C(2d) possesses a coarse surface, comprised of aggregated primary ultrasmall nanoparticles. The ED pattern corresponding to the entire particle on the [010] orientation confirms the singlecrystalline feature of Z-L0.4C-90°C(2d). This observation


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Journal of the American Chemical Society implies that the aggregation of protozeolitic primary nanoparticles might occur via an oriented-attachment manner to form single-crystalline architectures. Highmagnification images in Figures 3b and 3c show the continuous microporous framework with isolated domains of small mesopores (ca. 2-8 nm) evidenced by the lower contrast in the images. Figure 3d-f shows that the singlecrystalline Z-L0.4C-90(2d)/170(3h) possesses smoother crystal surface and larger mesopores compared with Z-L0.4C-90(2d).

Figure 3 (a) Low-magnification Cs-corrected STEM-ADF images of Z-L0.4C-90(2d), (b, c) high-magnification Cscorrected STEM-ADF images of region 1, (d) lowmagnification Cs-corrected STEM-ADF image of Z-L0.4C90(2d)/170(3h), (e, f) high-magnification Cs-corrected STEMADF images of region 2 and 3. Inset: corresponding ED patterns obtained from the entire particles The 27Al MAS NMR spectra show that all the samples consist of tetrahedral framework Al species (Figure S17). 29Si MAS NMR spectra show that the protozeolite consists of 6% defective [(HO)2Si(OT)2] (Q2), 16% [(HO)Si(OT)3] (Q3) units, and 78% [Si(OT)4] (Q4) units. Strikingly, the defective Q2 units disappear in Z-L0.4C-90(2d) and Z-L0.4C-90(2d)/170(3h), while Z-L0.4C-90(2d)/170(24h) that possesses only wellresolved Q4 units becomes completely defect-free.

The above-described analyses provide valuable insights into the formation mechanism of single-crystalline hierarchical nanozeolites. At the first step, the low temperature and concentrated gel condition favors nucleation over crystal growth. Initially, at 90°C for 1 day, the excess L-lysine (L-lysine/Si=0.4) confines the ultrasmall protozeolitic nanoparticles, preventing them from growing into larger crystals. Afterward, when the crystallization time is prolonged to 2 days, the primary protozeolites aggregate via an oriented-attachment manner, resulting in the formation of single-crystalline nanocrystals. Oriented aggregation has been reported as one of the main mechanisms for nanocrystal growth in other systems (e.g., FeOH, CuO, MoO3, and ZnO).11 The oriented aggregation of precursor nanoparticles during the evolution of silicalite-1 zeolite has also been proposed by Tsapstsis’s group.12 The orientated aggregation of protozeolite nanoparticles should be driven by minimization of the total Gibbs free energy of the system and followed by growth in the thermodynamically preferred orientation. It is expected that a perturbation to the system may cause the attachment of protozeolites across a mismatched interface and the formation of polycrystalline zeolite. This has been substantiated by some perturbation experiments, resulting in polycrystalline hierarchical zeolite nanocrystals (Figures S18 and S19). 13C MAS NMR spectra prove the existence of L-lysine in Z-L0.4C-90(1d) and Z-L0.4C90(2d) (Figure S20), which is due to the complexation between L-lysine and silicon species.13 L-lysine plays a critical role in the oriented aggregation of protozeolitic nanoparticles in a non-compact manner. Without addition or less amount of L-lysine in the synthetic gel led to the formation of compact crystals (Figures S3 and S4). At the second step, the high crystallization temperature (170°C) facilitates the intraparticle ripening of zeolite crystals. It is important to remark that during this process the crystal size remains unchanged at different periods because the nutrients are consumed at the first step. Therefore, intraparticle ripening becomes the predominant crystal growth behavior at high temperature, which was previously

Scheme 1 Proposed evolution process of single-crystalline and defect-free hierarchical nanozeolites. In the first step, protozeolitic primary nanoparticles are obtained at 90°C, and then undergo oriented aggregation in a non-compact manner induced by L-lysine, forming single-crystalline hierarchical nanozeolites with isolated mesopores; in the second step at 170°C, primary nanoparticles coalesce into larger ones through intraparticle ripening, consequently leading to evolution of pregenerated isolated mesopores to interconnected mesopores



observed in the synthesis of semiconductors or metals (CdSe, ZnS, and Au).14 Adjacent protozeolitic primary nanoparticles coalesced into larger ones through intraparticle ripening, which consequently led to the evolution of mesopores starting from initially isolated ones to final abundant interconnected ones. Such an intraparticle ripening was also observed for the evolution of Z-L0.4C-170, Z-L0.4C0-90/170, and Z-L0C0-90/170 (Figures S21-26), where the particle size remained unchanged and the crystal surface turned smoother. In contrast, a typical Ostwald ripening occurred during the evolution of Z-L0.4C0-170(3d) (Figures S27 and S28). Above experiments demonstrate that the change of kinetic factors may change the ripening process of zeolite crystals. Scheme 1 illustrates the proposed evolution process of the single-crystalline and defect-free hierarchical nanozeolites. This mechanism for the formation of singlecrystalline hierarchical nanozeolites is not only specific to Llysine, but also works with L-proline (Figure S29). The secondary pore size of hierarchical zeolites can be tuned by varying the second-step crystallization time and temperature (Figures S14, S16, S30, S31).

XRD patterns, SEM images, TEM images, DLS characterization, Low voltage HR-SEM images, HRTEM images, Cs-corrected STEM images, Pore size distribution, N2 adsorption/desorption, 27Al and 29Si solid-state MAS NMR spectra, catalytic conversion and product compositions. This material is available free of charge via the Internet at http://pubs.acs.org.

The hydrothermal stability of Z-L0.4C-90(2d)/170(24h) was assessed by exposing it to 10% water steaming at 600 °C for 5 h. After the treatment, there was no obvious change in XRD, N2 adsorption/desorption, and TEM, indicating its superior hydrothermal stability (Figures S32-34 and Table S2). We further tested the catalytic performance of Ni/Z-L0.4C90(2d)/170(24h) over stearic acid and palm oil HDO as compared with their conventional counterparts (Figures S3539 and Table S4). Ni/Z-L0.4C-90(2d)/170(24h) gave 85% conversion of stearic acid, which was much higher than those of conventional counterparts (Figure S40 and Table S5). The HDO capability of Ni/Z-L0.4C-90(2d)/170(24h) catalyst was further evaluated by using crude lipid palm oil with more complex components as reactant (Table S6). The palm oil HDO performance achieved a 100 wt% conversion with 83.05% liquid alkane yield, which nearly approached the theoretical yield of 85 wt% (Figure S41). These results suggest that the abundant interconnected mesopores of Ni/Z-L0.4C90(2d)/170(24h) facilitate the diffusion of bulky reagents and products.

We thank the National Key Research and Development Program of China (Grant 2016YFB0701100), the National Natural Science Foundation of China (Grant 21835002, 21621001, and 21850410448), and the 111 Project (B17020) for supporting this work. This work is partially supported by CℏEM, SPST, ShanghaiTech (Grant 02161943).

In summary, we have developed a facile amino acidassisted strategy for constructing hierarchically nanosized ZSM-5 that are featured by single-crystalline and defect-free frameworks with abundant interconnected mesopores. This was achieved by oriented aggregation of protozeolite nanoparticles formed at low temperature, followed by intraparticle ripening process at high temperature. The small L-lysine molecules not only served as a crystal growth inhibitor but also facilitated the orientated aggregation of protozeolite nanoparticles in a non-compact manner. On the other hand, intraparticle ripening that occurred at high temperature was responsible for the defect-free hierarchical nanozeolites with abundant interconnected mesopores. This kinetic-modulated crystallization strategy opens a new way to the fabrication of high-quality single-crystalline hierarchical nanozeolites, thus promising their practical industrial applications in catalytic conversions of bulky molecules.

ASSOCIATED CONTENT Supporting Information

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected].

ORCID

Qiang Zhang: 0000-0002-2837-8473 Alvaro Mayoral: 0000-0002-5229-2717 Osamu Terasaki: 0000-0001-5803-0817 Jihong Yu: 0000-0003-1615-5034

Notes

The authors declare no competing financial interest.

ACKNOWLEDGEMENT

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