Sustainable synthesis of hierarchical MFI zeolite from mesoporous HMS and catalytic application

Sustainable synthesis of hierarchical MFI zeolite from mesoporous HMS and catalytic application | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Sustainable synthesis of hierarchical MFI zeolite from mesoporous HMS and catalytic application Longyang Wang, Zihao Yang, Xin Wang, Tong Wu, Changzi Jin, Rui Wang, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8692112/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 4 You are reading this latest preprint version Abstract Constructing hierarchical structure in conventional zeolites is a promising means to overcome intrinsic shortcomings of this type of microporous material. In this research, a novel synthesis strategy for hierarchical zeolite was presented. By utilizing mesoporous HMS as silica source, MFI aluminosilicate with mesoporosity was successfully prepared through sustainable process without organic template or large amounts of solvent. The obtained products were characterized by a series of techniques, including X-ray diffraction, transmission electronic microscopy, N 2 physical adsorption, X-ray fluorescence and NH 3 temperature programmed desorption. It has been shown that as-synthesized and calcined HMS had generated MFI zeolite with different mesoporosity, based on which the different synthesis mechanisms for hierarchical products were proposed. The alkylamine dose not impede the sustainable synthesis of MFI zeolite, which endow the availability of HMS for green synthesis of hierarchical zeolite. After loaded with platinum, the obtained hierarchical bifunctional catalysts show higher activity but lower isomers selectivity in hydroisomerization of n -heptane compared to mono-microporous counterpart. In addition, the mesoporosity of the catalysts had led to the higher multi-branched isomers productivity. Hierarchical MFI zeolite HMS Sustainable synthesis Hydroisomerization Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Introduction The crystalline aluminosilicate zeolites are a class of important inorganic materials, which possess abundant porosity, huge surface area, regulable acidity and excellent stability and are widely used in many industrial processes, such as heterogeneous catalysis, adsorption and separation, ion exchange and so on [1–7]. As typical member of aluminosilicate zeolites, the MFI-type ZSM-5 with 10-ring three-dimensional channel has attracted numerous attentions for its outstanding performance in petrochemical and fine chemicals processing [8–13]. However, the pore sizes of ZSM-5 and most other aluminosilicate zeolites are usually less than 1.0 nm, which have caused serious diffusional problem, especially in the processes with bulky molecules involved [14]. Therefore, introducing the mesopores or macropores into the microporous zeolites to construct hierarchical matrix has been regarded as one of the most effective strategies to facilitate the mass transfer of the materials [15–21]. To date, the researchers have done a large number of research on the preparations of hierarchical zeolites, which can be classified into two protocols of bottom-up and top-down [22, 23]. In the former protocol, the thermally decomposable substances, such as surfactants, polymers or carbon materials are usually added into the synthetic system of zeolites as template (soft- or hard-template) [24–27]. The hierarchical structure can be formed by removing these templates from the crystallized zeolite products. During this process, effective templates and suitable synthetic technology are crucial to obtain the hierarchical zeolites. The top-down protocol is the post-treatment of microporous zeolites by desilication or dealumination to yield the hierarchical structure [28–30]. Although no special templates are required in top-down synthesis route, it is not easy to control the dissolution of initial zeolite, as well as the generation of hierarchical porosities. In addition, the loss of zeolite body is inevitable in this top-down process. Therefore, developing more facile and effective synthesis strategies for hierarchical zeolites is still one of the research focuses currently. In view of the economic and environmental shortcomings of conventional hydrothermal synthesis of zeolites, the sustainable synthesis method without organic templates or solvents has attracted more and more attentions [31–36]. Moreover, the green synthesis ideas have also been extended to the fabrication of hierarchical zeolites in recent years [37]. For example, the hierarchical zeolites can be prepared in mesoporogen-free system by finely controlling synthesis condition or appropriate pretreatment to construct porous raw materials [38, 39]. Xiao and co-workers had synthesized hierarchical aluminosilicate and silicoaluminophosphate zeolites via sustainable processes with neither solvent nor mesoporogen, during which the gaseous expansion in crystallization process may be responsible for the formation of mesopores [40]. In addition to the conventional commercial silica and aluminia source, some natural materials such as kaolin, diatomite, rectorite and rice husk ash had also been utilized to synthesize hierarchical zeolites, which are described as sustainable source approach [41–43]. The sustainable approaches without organic templates or solvents reduce the costs and the noxious pollutants and offer distinct advantages over conventional synthesis processes. However, the generation process of hierarchical structure may be different in various sustainable synthesis approaches. Therefore, it is desired to develop novel efficient sustainable synthesis method for hierarchical zeolites and explore the formation mechanism of hierarchical structure as well. In this work, we reported a novel organic template-free and solvent-free sustainable synthesis approach for hierarchical ZSM-5 zeolite with mesoporous silica HMS as silica source. The mesoporous silica source before and after calcination had generated hierarchical zeolite with different porous structure. The long-chain alkylamine occluded in HMS silica source did not hinder the formation of MFI topology and would serve as mesoporogen for hierarchical zeolite product. The hierarchical ZSM-5 was functionalized with Pt sites to construct bifunctional catalysts, which exhibited excellent performance in hydroisomerization of n -heptane. Experimental 2.1 Chemicals Tetraethylorthosilicate (TEOS), dodecylamine (DDA), hexadecylamine (HDA), and chloroplatinic acid (H 2 PtCl 6 ·6H 2 O) were purchased from Beijing Innochem Science and Technology Ltd. Ethanol (EtOH), sodium aluminate (NaAlO 2 ), sodium hydroxide (NaOH) and ammonium chloride (NH 4 Cl) were purchased from Tianjin Damao Chemical Co. Silica gel was purchased from Qingdao Xinchanglai Silica Gel Ltd. All the chemicals were of analytical grade and used as received without any purification. The distilled water was homemade. 2.2 Synthesis of mesoporous HMS The mesoporous silica HMS was prepared according to the published approach with some modification [44]. Typically, 2.40 g DDA (or 3.13 g HDA) was dissolved into 19 mL ethanol, followed by the addition of 31.5 mL water under continuous stirring. Then, 10 g TEOS was added dropwise into the solution and the obtained mixture was further stirred at room temperature for 18 h. The solid product was collected by filtration and dried at 100 o C. The as-synthesized HMS (as-HMS) was calcined at 600 o C under air atmosphere for 6h to remove the organic components, and the calcined HMS (ca-HMS) can be obtained. 2.3 Synthesis of hierarchical ZSM-5 The hierarchical ZSM-5 was synthesized through sustainable quasi-solid phase approach in the absence of organic template or abundant solvent [45]. Typically, the mesoporous HMS (as-synthesized or calcined samples), NaAlO 2 , NaOH and H 2 O were mixed together as molar ratio of 1.0SiO 2 : 0.025Al 2 O 3 : 0.072Na 2 O : 2.0H 2 O and grinded for 10 min in agate mortar. The final mixture was transferred into Teflon-lined autoclave and heated at 170 o C for 48 h. The products from as-synthesized HMS need to be calcined at 600 o C for 6 h to remove the alkylamine. The H-type zeolites were prepared by the ion-exchange of Na-type counterparts with NH 4 Cl (1M) aqueous solution at 80 o C for 6 h, followed by calcination at 550 o C in air for 4 h. 2.4 Synthesis of bifunctional catalysts The Pt/ZSM-5 bifunctional catalysts were prepared via incipient-wetness impregnation method with H 2 PtCl 6 as Pt precursor. The theoretical Pt loading of bifunctional catalysts is 0.5%. 2.5 Characterization Small and wide-angle X-ray diffraction (XRD) patterns were measured in Bruck D8 Advance powder X-ray diffractometer using Cu Kα radiation. Transmission electronic microscopy (TEM) images were obtained on JEM-2100 electronic microscope with an accelerating voltage of 200 kV. Nitrogen physical adsorption/desorption isotherms were recorded on BSD-660M A6M physical adsorption analyzer. The specific surface areas were calculated using the BET method and the pore size distributions were calculated from the adsorption branches of the isotherms by using NLDFT method. Ammonia temperature programmed desorption (NH 3 -TPD) measurements were performed on Quantachrome TPD/TDR-Pulsar chemisorption analyzer in the range of 150–600°C at a ramp rate of 20°C min − 1 . The SiO 2 /Al 2 O 3 ratio of the samples was calculated based on the analysis on Bruker D8 Tiger X-ray fluorescence (XRF) spectrometer. 2.6 Hydroisomerization reaction of n -heptane The hydroisomerization of n -heptane were operated on a fixed-bed stainless steel reactor at atmospheric pressure. Before reaction, the Pt/ZSM-5 bifunctional catalysts were treated by H 2 flow at 400°C for 2h, and then was cooled to reaction temperature. The n -heptane was fed into reactor with HPLC pump at a weight hourly space velocity (WHSV) of 2.0 h − 1 and the H 2 was controlled by mass flowmeter to fix the molar ratio of H 2 / n -heptane at 10. The reaction products were on-line analyzed via gas chromatography (Techcomp GC7890) equipped with a TM-PONA capillary column and FID detector. Results and discussion 3.1 Synthesis and characterization of hierarchical ZSM-5 The sustainable synthesis approach for ZSM-5 zeolites herein is an organotemplate-free quasi-solid phase process by using mesoporous silica (HMS) and NaAlO 2 as silica and aluminum source, respectively. Figure 1 shows the wide-angle XRD patterns of as-synthesized samples. Obviously, all the obtained samples from either as-synthesized or calcined HMS possessing typical MFI topology. Our previous report confirmed the availability of solid silica gel in the synthesis of MFI zeolites without the assistance of OSDA or solvent [45]. Current result indicates that the silica source of mesoporous HMS is also effective in this sustainable synthesis process. Even the alkylamine (DDA or HDA) occluded in the mesopores of HMS did not significantly disrupte the formation of zeolite product. In addition, it should be noted that the obtained zeolites do not exhibit any diffraction signals in small-angle region, which indicates that the ordered mesoporous channel of HMS predecessor had not remained in final zeolite products (Figure S1 ). Figure 2 presents the TEM images of the obtained MFI zeolites from different silica sources. It is interesting that the as-synthesized and calcined HMS generated the zeolite products with different porous structure. For the calcined HMS-derived samples (Fig. 2 a and c), the vesicular mesopores with size of a few nanometers to tens of nanometers can be observed. However, similar porous feature had not been found in the samples from as-synthesized HMS containing alkylamine (Fig. 2 b and d). Different from the synthesis system reported by Xiao’s group, where large amounts of NH 3 can be generated by the reaction of Na 2 SiO 3 and NH 4 Cl, the starting raw materials herein (HMS, NaAlO 2 and NaOH) will not generate enough gaseous products [40]. Therefore, the formation of mesoporosity in calcined HMS-derived zeolites might be due to other reasons. In fact, our previous report had disclosed the distinct porous structure of MFI zeolites from different silica sources via the solvent-free process [45]. Compared to single microporous product from bulky solid silica gel, the silica nanospheres had yielded hierarchical zeolite, which indicated that the particle size of silica sources may have an impact on the porous structure of final product. Back to current research, the calcined HMS turned into hierarchical zeolite, possibly because the precursors tend to break into small pieces during grinding process compared to as-synthesized ones with alkylamine filling in mesopores. In addition, the alkylamine-removed calcination process may also lead to some of the bulky silica matrix break (Figure S2). During the solvent-free synthesis process, the interspace of tiny particles of silica sources more likely to be reserved and form the mesoporosity of final zeolite products. It is worth noting that although the as-synthesized HMS did not generate zeolites with obvious mesoporosity, greater magnification of TEM images indicate that the products possess wormlike porosity (Fig. 2 b and d, inset), which is similar to the HMS predecessor (Figure S2). This phenomenon implies that the alkylamine (DDA or HDA) in the channel of HMS may be involved into zeolite grain during this quasi-solid phase synthesis process. Then, after calcining to remove the organic alkylamine, the zeolite products with additional porosities had been obtained. However, it is inevitable that the mesopores of HMS shrink during the crystallization process, which lead to smaller pores in zeolite products than the amorphous HMS silica source. The textural properties of synthesized zeolites were further tested by N 2 physical adsorption measurement. Figure 3 presents the isotherms of the obtained samples. Apparently, all the ZSM-5 zeolites show the feature of type-I isotherm with obvious N 2 uptake at low pressure region (P/P 0 < 0.1), which are due to the intrinsic microporous crystallite of zeolite. For the ca-HMS-derived zeolites, the hysteresis can be found at P/P 0 of 0.5 ~ 1.0 (Fig. 3 a and b), indicating the presence of additional bigger pores in the samples, which is consistent with the TEM results (Fig. 2 a and c). By comparison, the isotherms of samples from as-HMS are relatively flat at higher pressure region (Fig. 3 c and d). Instead, a weak step at P/P 0 of around 0.1 had been observed, which is due to N 2 filling in the pores with uniform pore size and is similar to type-IV isotherms assigning to mesoporous materials. The pore size distribution of the samples provides more intuitive information. As Fig. 4 has shown, the as-HMS-derived zeolites exhibit wide distribution centered around 1.5 ~ 1.7 nm, while the samples from ca-HMS do not exhibit any obvious distribution at this region. Therefore, these “big micropores” in as-HMS-derived zeolites might arise from the mesopores of HMS for the accommodation of alkylamine. However, the pore size of generated “big micropores” in zeolite products is smaller than the HMS predecessor (Figure S3). Moreover, the HMS-HDA with bigger mesopores did not generate the “bigger micropores” in final zeolite product. As stated above, the reason is probably that the mesoporous structure of HMS collapsed during crystallization process and lead to the uncontrolled shrinkage of original mesopores. In addition, as Table 1 has shown, both specific surface area and pore volume of as-HMS-derived zeolites are higher than that of samples generated from ca-HMS, which indicate that these “big micropores” are more helpful to improve the textural properties of samples. Table 1 Textural properties of synthesized zeolites Silica source SiO 2 /Al 2 O 3 molar ratio Surface area (m 2 /g) Pore volume (cm 3 /g) as-HMS-DDA 59 378 0.17 ca-HMS-DDA 50 255 0.15 as-HMS-HDA 55 398 0.18 ca-HMS-HDA 56 265 0.14 According to the results described above, the formation mechanism of hierarchical MFI zeolites from mesoporous HMS can be represented in Fig. 5 . For the bulky silica source (such as solid silica gel), the conventional microporous zeolite has been obtained during the quasi-solid phase synthesis. Although the silica sources possess mesoporous structure (Figure S4), the mesoporosity cannot be reserved in final zeolite products without effective supports. When the silica source possesses tiny particles (Stӧber SiO 2 sphere or ca-HMS), the interspaces of particles are likely to evolve into the mesoporosity of final zeolite products, even if the silica source is nonporous. It should be noted that the formation of ca-HMS with tiny particles possesses fortuity and uncontrollability, as well as the corresponding synthesis process for hierarchical zeolite. As to the as-synthesized HMS with alkylamine template in the mesopores, the original mesoporous structure will collapse during crystallization process. Because of the supporting effect of alkylamine, however, the mesoporosity of HMS can be reserved in zeolite product, just shrank to a certain degree. Based on the experimental results and proposed synthetic mechanism, the feasibility of mesoporous materials, such as MCM-41 with CTAB as template, for synthesis of hierarchical zeolites was also investigated. From the XRD analysis showed in Fig. 6 , one can find that compared to the HMS, the product with very low MFI topology crystallinity had been generated by using as-synthesized MCM-41 as silica source. The broad signal at 2θ of 18-25 o is assigned to the amorphous silica, which indicates that CTAB might have negative effect on the OSDA-free quasi-solid phase crystallization process. In order to verify this point, CTAB and DDA were respectively added into the synthetic system with solid silica gel as silica source. Regardless of the availability of solid silica gel for the sustainable synthesis of ZSM-5, the MFI zeolite cannot be obtained with the addition of CTAB (Fig. 6 b). By comparison, the sample from DDA-involved system possesses complete MFI topology, though there is some cristobalite impurity displaying the diffraction peak at 21.7 o (Fig. 6 c). Therefore, the alkylamine has lesser impact on the sustainable synthesis of MFI zeolite without OSDA or solvent, which corroborated the feasibility of HMS for fabrication of hierarchical zeolite during this process. 3.2 Catalytic application of prepared hierarchical zeolites The Pt/zeolite bifunctional catalysts with the prepared hierarchical ZSM-5 as acid support were synthesized through incipient-wetness impregnation method. Figure 7 presents the TEM images of the prepared catalysts. It can be found that the Pt particle sizes at different zeolite supports are also different. Although the zeolites from as-HMS possess higher specific surface areas than ca-HMS-derived ones (Table 1 ), the former-generated catalysts show Pt particle size of 3-15nm (Fig. 7 a,c), which are bigger than that of latter-involved system (~ 3nm, Fig. 7 b,d). Considering same Pt theoretic content (0.5wt%) in all catalysts, the different particle size might be related with the porous structure of zeolite supports. The XRD patterns of the synthesized catalysts is showed in Fig. 8 . Obviously, the catalysts from as-HMS-derived zeolites exhibit a weak diffraction peak at 39.7 o , which can be indexed to the crystalline plane (111) of cubic platinum crystal (00-001-1190). The catalysts based on ca-HMS-derived zeolites do not show any characteristic Pt-related diffraction peaks (Fig. 8 c,d), which may be due to their small Pt particle size and in accordance with the TEM results (Fig. 7 ). Figure 9 presents the NH 3 -TPD profiles of the synthesized bifunctional catalysts. It can be observed that all the catalysts exhibit the profiles consisting of two desorption peaks centered at 150 o C and 400 o C, which are ascribed to weak and strong acid sites, respectively. According to the XRF results, the alumina content in the zeolite supports is similar and giving the SiO 2 /Al 2 O 3 molar ratio of 50 ~ 59 (Table 1 ). Therefore, it is expectable that all the obtained catalysts possess similar acid properties. However, the different intensity of adsorption peak in Fig. 9 indicates that there are some differences among the acid amount for synthesized catalysts. The catalytic performance of the synthesized bifunctional catalysts for the hydroisomerization of n -heptane was investigated and the results are showed in Fig. 10 . It has been found that all the catalysts are inactive at low reaction temperature and exhibit the conversion less than 15% at the temperature lower than 220 o C (Fig. 10 a). The activity for all catalysts increased with the rise of reaction temperature. Most catalysts give the conversion of n -heptane higher than 80% when the temperature reaches 280 o C. Except the catalyst from as-HMS(HDA)-derived zeolite, the gap among the activity of other catalysts is not too much. The highest activity of as-HMS(HDA)-derived catalyst might be related with its high acid amount (Fig. 9 ). Figure 10 b and c show the selectivities for C 7 isomers and cracked products over the synthesized catalysts at different temperature. Obviously, with the increase of temperature, the isomers selectivity over most catalysts declined quickly, while the cracked products increased. Especially at high temperature (280 o C), the cracked reactions dominate (> 95%). It should be noted that all the investigated catalysts exhibit the lower isomers selectivity of less than 50% even at lower reaction temperature, which is different from other reported catalytic system [46–49]. In fact, our previous reports had already demonstrated the inferior catalytic performance of sustainable synthesized MFI zeolite to that of conventional ones for hydroisomerization of n -heptane, even though their textural properties are similar [8, 45]. For the MWW zeolite catalysts, however, this is not the case [50]. So, the influence laws over different zeolite type might be distinct for this hydroisomerization reaction. According to the published literature, many factors are influential for the catalytic performance of zeolite-based catalysts, such as zeolitic topology, specific surface area, porous structure, acidity and metal character. The final catalytic performance of catalysts is the result of integrate all these factors. Table 2 Detailed catalytic results over different catalysts at 240 o C Catalytic results Catalyst with MFI supports from different silica source as-HMS (DDA) ca-HMS (DDA) as-HMS (HDA) ca-HMS (HDA) Silica solid gel Conversion (%) 26.74 24.55 59.28 39.42 7.89 Isomers selectivity 2-Methyl Hexane 9.96 19.14 7.83 5.61 39.23 3-Methyl Hexane 8.51 12.22 9.10 5.28 18.99 3-Ethyl Pentane 0.82 0.84 0.53 0.44 0.77 2, 2-Dimethylpentane < 0.01 < 0.01 < 0.01 < 0.01 0.03 2, 4-Dimethylpentane 0.19 0.23 0.29 0.10 0.29 3, 3-Dimethylpentane < 0.01 0.01 < 0.01 < 0.01 0.01 Total 19.49 32.45 17.76 11.44 59.34 Cracked selectivity Methane < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Ethane < 0.01 0.01 0.02 0.02 0.01 Propane 30.02 25.15 32.01 34.51 14.45 Iso-Butane 38.21 33.77 43.29 44.89 21.03 Butane 3.55 2.21 2.14 3.04 0.45 Pentane 4.32 2.55 2.31 3.11 0.70 2-Methyl Pentane 0.51 0.40 0.39 0.29 0.14 3-Methyl Pentane 0.18 0.15 0.20 0.12 0.06 Hexane 2.38 1.88 1.14 1.53 1.01 Total 79.16 66.14 81.49 87.51 37.85 Others selectivity Methyl Cyclohexane 0.75 0.62 0.51 0.55 1.03 Ethyl Cyclopentane 0.51 0.57 0.22 0.36 1.17 Toluene < 0.01 < 0.01 0.02 0.02 0.02 Unkown components < 0.01 < 0.01 < 0.01 < 0.01 0.59 Total 1.26 1.20 0.75 0.93 2.81 Detailed catalytic results for the synthesized catalysts are listed in Table 2 . In addition, the catalyst based on mono-microporous ZSM-5 from solid silica gel was also compared to further explore the impact of hierarchical structure on the catalytic performance of catalysts. It can be found that the hierarchical catalysts from HMS possess higher activity and exhibit reactant conversion of more than 20% at 240 o C. By contrast, the mono-microporous catalyst from solid silica gel shows the conversion as low as 7.89% at same temperature, while a higher isomers selectivity. All the investigated catalysts show similar product types, namely the mono-branched 2-/3-methylhexanes and propane/isobutane dominate the isomers and cracked products, respectively, which is a common characteristic of 10-ring zeolite-based catalyst. There is no significant regularity in the different product selectivities of four hierarchical catalysts. Sazama et al had confirmed that the hierarchical structure had no influence on the shape selectivity of zeolite catalyst for hydroisomerization of hexane and the intrinsic zeolitic channel play decisive role in the formation of isomer products [51]. In current research, however, the hierarchical catalysts had generated higher multi-branched isomers contents than mono-microporous counterpart (Fig. 11 ). In general, the formation of muti-branched isomers (> C 6 ) is restricted over 10-ring channel zeolite for spatial confinement. The slightly higher multi-branched isomers products contents of HMS-derived catalysts maybe related with their hierarchical structure, especially the catalysts from as-HMS. These results are also significant to the synthesis of high-performance catalysts for hydroisomerization of linear alkanes. Conclusion In summary, MFI zeolite with hierarchical structure was successfully synthesized through sustainable OSDA/solvent-free process with mesoporous HMS as silica source. Both as-synthesized and calcined HMS can generate hierarchical zeolite but the mesoporosity of products and corresponding formation mechanism are different. The alkylamine in the as-synthesized HMS does not only impede the crystallization process, but can be involved in zeolite particles and conduce to the reservation of mesoporosity of HMS. The hierarchical structure of calcined HMS-derived zeolites might be due to the tiny particles of silica source. After modified with Pt metal, the obtained hierarchical bifunctional catalysts showed higher activity but lower isomers selectivity in hydroisomerization of n -heptane compared to the mono-microporous counterpart. The higher muti-branched isomers contents over HMS-derived catalysts also verified their hierarchical structure. This work not only develop novel strategy for sustainable synthesis of hierarchical zeolite, but also is instructive to fabricate effective catalysts for hydroisomerization of linear alkanes. Declarations Author Contribution This manuscript was written through contributions from all authors. LW, CJ and RW wrote the main manuscript text. LW finished the preparation of zeolites. ZY finished catalytic tests. LW, XW and TW finished the characterization and prepared the figures. HJ participated in the discussion and analysis of experiment results. All authors reviewed the manuscript and approved the final version. Acknowledgement This work was financial supported supports by the Talent Scientific Research Fund of LNPU (2020XJJL-016) and the Project of the Educational Department of Liaoning Province (LJ212410148035). References Jae J, Tompsett GA, Foster AJ, Hammond KD, Auerbach SM, Lobo RF, Huber GW (2011) Investigation into the shape selectivity of zeolite catalysts for biomass conversion. J Catal 279: 257-268. https://doi.org/10.1016/j.jcat.2011.01.019 Rahimi N, Karimzadeh R (2011) Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: A review. Appl Catal A-Gen 398: 1-17. https://doi.org/10.1016/j.apcata.2011.03.009 Olsbye U, Svelle S, Bjorgen M, Beato P, Janssens TVW, Joensen F, Bordiga S, Lillerud KP (2012) Conversion of methanol to hydrocarbons: How zeolite cavity and pore size controls product selectivity. Angew Chem Int Ed 51: 5810-5831. https://doi.org/10.1002/anie.201103657 Demirci S, Ustaoglu Z, Yilmazer GA, Sahin F, Baç N (2014) Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms. Appl Biochem Biotech 172: 1652-1662. https://doi.org/10.1007/s12010-013-0647-7 Shwan S, Skoglundh M, Lundegaard LF, Tiruvalam RR, Janssens TVW, Carlsson A, Vennestrom PNR (2015) Solid-state ion-exchange of copper into zeolites facilitated by ammonia at low temperature. ACS Catal 5: 16-19. https://doi.org/10.1021/cs5015139 Pérez-Botella E, Valencia S, Rey F (2022) Zeolites in adsorption processes: state of the art and future prospects. Chem Rev 122: 17647-17695. https://doi.org/10.1021/acs.chemrev.2c00140 Yue ML, Bu KK, Shen W, Xu HL, Huang Z (2026) Stable Ga-MFI zeolite for propane dehydroaromatization constructed by healing Silanol-defect in framework. J Colloid Inter Sci 708. https://doi.org/10.1016/j.jcis.2025.139807 Zhu MX, Li HQ, Wang X, Wang LY, Wang R, Jiang H, Jin CZ (2025) Spatial configurational construction of Pt-ZSM-5 bifunctional catalysts for hydroisomerization of n -heptane. Catal Surv Asia 29: 155-166. https://doi.org/10.1007/s10563-025-09446-5 Kandula M, Gutta N, Aytam HP, Perupogu V, Manda K, Akula V (2022) Rice husk ash derived SiO 2 for template free synthesis of H-ZSM-5 support for Ni catalyst: investigation on non-oxidative CH 4 cracking for clean H 2 production. Catal Surv Asia 26: 336-345. https://doi.org/10.1007/s10563-022-09365-9 Raghav H, Sah L, Joshi B, Tiwari R, Lama P, Sarkar B, Bal R (2025) Conversion of waste plastic into low-carbon olefins: directly producing C-C light olefins from low-density polyethylene waste using a Cu/ZSM-5 catalyst. Green Chem 27: 15192-15199. https://doi.org/10.1039/d5gc04106f Qin WC, Li CY, Fu TJ, Cao RW, Wu XQ, Liu YY, Meng FH, Zhan GW, Li Z (2026) Integrating ZSM-5 catalyst with controllable crystal size on macroporous biomass platform for benzene methylation with CO 2 /H 2 . Fuel 411: 138011. https://doi.org/10.1016/j.fuel.2025.138011 Yousefi MR, Rahimi S, Rostamizadeh M (2021) Effective high silica ZSM-5 nanocatalyst including Fe and B promoters for production of high value petrochemicals in plastic upgrading process. J Anal Appl Pyrol 156. https://doi.org/10.1016/j.jaap.2021.105108 Mohammadparast F, Halladj R, Askari S (2015) The crystal size effect of nano-sized ZSM-5 in the catalytic performance of petrochemical processes: A review. Chem Eng Commun 202: 542-556. https://doi.org/10.1080/00986445.2014.952815 Li BC, He Y, Geng R, Shao JB, Wei CL, Qin ZF, Wang JG, Fan WB, Dong M (2025) Progress on enhancing the resistance to deactivation of Zn-containing ZSM-5 catalysts for light hydrocarbon aromatization. Chemcatchem 17. https://doi.org/10.1002/cctc.202500085 Chen LH, Sun MH, Wang Z, Yang WM, Xie ZK, Su BL (2020) Hierarchically structured zeolites: from design to application. Chem Rev 120: 11194-11294. https://doi.org/10.1021/acs.chemrev.0c00016 Zhang CS, Lu FX, Zhao JC, Wen S, Sun B, Jiang J (2026) Minute-scale synthesis of hierarchical and nanosized ZSM-5 zeolites with high space-time yields. Chem Eng Sci 321: 122931. https://doi.org/10.1016/j.ces.2025.122931 Jiang JX, Jorda JL, Yu JH, Baumes LA, Mugnaioli E, Diaz-Cabanas MJ, Kolb U, Corma A (2011) Synthesis and structure determination of the hierarchical meso-microporous zeolite ITQ-43. Science 333: 1131-1134. https://doi.org/10.1126/science.1208652 Peng P, Gao XH, Yan ZF, Mintova S (2020) Diffusion and catalyst efficiency in hierarchical zeolite catalysts. Natl Sci Rev 7: 1726-1742. https://doi.org/10.1093/nsr/nwaa184 Qi S, Liu GZ, Wang JL, Zhang HD, Cheng P (2026) L-histidine-controlled synthesis of hierarchical HZSM-5 zeolite with excellent stability and propylene selectivity for 1-butene catalytic cracking. ChemistrySelect 11. https://doi.org/10.1002/slct.202505457 Gueudré L, Milina M, Mitchell S, Pérez-Ramírez J (2014) Superior mass transfer properties of technical zeolite bodies with hierarchical porosity. Adv Funct Mater 24: 209-219. https://doi.org/10.1002/adfm.201203557 Zhang JY, Wang H, Qin YC, Song LJ (2021) Progress in characterization strategies mass transfer mechanism of hierarchical zeolite. J Petrochem Univ 34: 1-8. https://doi.org/10.3969/j.issn.1006-396X.2021.04.001 Bai RS, Song Y, Li Y, Yu JH (2019) Creating hierarchical pores in zeolite catalysts. Trends Chem 1: 601-611. https://doi.org/10.1016/j.trechm.2019.05.010 Jia XC, Khan W, Wu ZJ, Choi J, Yip ACK (2019) Modern synthesis strategies for hierarchical zeolites: Bottom-up versus top-down strategies. Adv Powder Technol 30: 467-484. https://doi.org/10.1016/j.apt.2018.12.014 Wang LF, Zhang Z, Yin CY, Shan ZC, Xiao FS (2010) Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic polymers. Micropor Mesopor Mat 131: 58-67. https://doi.org/10.1016/j.micromeso.2009.12.001 Song YD, Hua ZL, Zhu Y, Zhou XX, Wu W, Zhang LL, Shi JL (2012) An in situ carbonaceous mesoporous template for the synthesis of hierarchical ZSM-5 zeolites by one-pot steam-assisted crystallization. Chem-Asian J 7: 2772-2776. https://doi.org/10.1002/asia.201200744 Choi M, Cho HS, Srivastava R, Venkatesan C, Choi DH, Ryoo R (2006) Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity. Nat Mater 5: 718-723. https://doi.org/10.1038/nmat1705 Xiao FS, Wang LF, Yin CY, Lin KF, Di Y, Li JX, Xu RR, Su DS, Schlogl R, Yokoi T, Tatsumi T (2006) Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. Angew Chem Int Ed 45: 3090-3093. https://doi.org/10.1002/anie.200600241 Verboekend D, Pérez-Ramírez J (2011) Design of hierarchical zeolite catalysts by desilication. Catal Sci Technol 1: 879-890. https://doi.org/10.1039/c1cy00150g Zhao LA, Gao JS, Xu CM, Shen BJ (2011) Alkali-treatment of ZSM-5 zeolites with different SiO 2 /Al 2 O 3 ratios and light olefin production by heavy oil cracking. Fuel Process Technol 92: 414-420. https://doi.org/10.1016/j.fuproc.2010.10.003 Yu LL, Huang SJ, Miao S, Chen FC, Zhang S, Liu ZN, Xie SJ, Xu LY (2015) A facile top-down protocol for postsynthesis modification of hierarchical aluminum-rich mfi zeolites. Chem-Eur J 21: 1048-1054. https://doi.org/10.1002/chem.201404817 Ren WG, Li J, Han LN, Wang B, Wang JC, Chang LP, Bao WR (2024) One-step synthesis of zeolite ZSM-5 from perlite tailings by crystal seed solution assisted method. Fuel 374. https://doi.org/10.1016/j.fuel.2024.132489 Jablonska M, Palcic A, Lukman MF, Wach A, Bertmer M, Poppitz D, Denecke R, Wu XC, Simon U, Pöppl A, Gläser R (2023) OSDA-free seeded Cu-containing ZSM-5 applied for NH 4 -SCR-DeNO x . ACS Omega 8: 41107-41119. https://doi.org/10.1021/acsomega.3c03721 Liu P, Wu QM, Yan KP, Wang L, Xiao FS (2022) Solvent-free synthesis of FAU zeolite from coal fly ash. Dalton T 52: 24-28. https://doi.org/10.1039/d2dt03196e Yin HT, Wang W, Li YX, Wen H, Chen S, Jiang NZ (2024) An eco-friendly method for the scale-up synthesis of ZSM-5 Zeolite. Micropor Mesopor Mat 365. https://doi.org/10.1016/j.micromeso.2023.112907 Jin YY, Sun Q, Qi GD, Yang CG, Xu J, Chen F, Meng XJ, Deng F, Xiao FS (2013) Solvent-free synthesis of silicoaluminophosphate zeolites. Angew Chem Int Ed 52: 9172-9175. https://doi.org/10.1002/anie.201302672 Deng LF, Lou CY, Wu QM, Liu XL, Niu J, Du XH, Xu ST, Wang L, Liu ZM, Yu JH, Xiao FS (2025) Insights into the wastewater-free synthesis of zeolites. J Am Chem Soc 147: 42901-42908. https://doi.org/10.1021/jacs.5c15625 Maghfirah A, Ilmi MM, Fajar ATN, Kadja GTM (2020) A review on the green synthesis of hierarchically porous zeolite. Mater Today Chem 17. https://doi.org/10.1016/j.mtchem.2020.100348 Yue YY, Gu LL, Zhou YN, Liu HY, Yuan P, Zhu HB, Bai ZS, Bao XJ (2017) Template-free synthesis and catalytic applications of microporous and hierarchical ZSM-5 zeolites from natural aluminosilicate minerals. Ind Eng Chem Res 56: 10069-10077. https://doi.org/10.1021/acs.iecr.7b02531 Kadja GTM, Mukti RR, Liu ZD, Rilyanti M, Ismunandar, Marsih IN, Ogura M, Wakihara T, Okubo T (2016) Mesoporogen-free synthesis of hierarchically porous ZSM-5 below 100 °C. Micropor Mesopor Mat 226: 344-352. https://doi.org/10.1016/j.micromeso.2016.02.007 Zhang CS, Wu QM, Lei C, Pan SX, Bian CQ, Wang L, Meng XJ, Xiao FS (2017) Solvent-free and mesoporogen-free synthesis of mesoporous aluminosilicate ZSM-5 zeolites with superior catalytic properties in the methanol-to-olefins reaction. Ind Eng Chem Res 56: 1450-1460. https://doi.org/10.1021/acs.iecr.7b00062 Alaba PA, Sani YM, Daud WMaW (2015) Synthesis and characterization of hierarchical nanoporous HY zeolites from acid-activated kaolin. Chin. J. Catal. 36: 1846-1851. https://doi.org/10.1016/S1872-2067(15)60962-7 Zhang CQ, Li SQ, Bao SC (2018) A facile and green method for the synthesis of hierarchical ZSM-5 zeolite aggregates from rice husk ash. Research on Chemical Intermediates 44: 3581-3595. https://doi.org/10.1007/s11164-018-3326-z Hartanto D, Kurniawati R, Pambudi AB, Utomo WP, Leaw WL, Nur H (2019) One-pot non-template synthesis of hierarchical ZSM-5 from kaolin source. Solid State Sci 87: 150-154. https://doi.org/10.1016/j.solidstatesciences.2018.11.015 Li SY, Huang B, Jin CZ, Wang R, Jiang H, Yang GS, Huang SJ (2023) Selective conversion of ethanol and acetaldehyde to 1,3-butadiene over Zr-HMS catalysts. Catal Surv Asia 27: 207-216. https://doi.org/10.1007/s10563-023-09390-2 Zhu MX, Xu WQ, Wang LY, Wang R, Jiang H, Jin CZ (2024) Sustainable synthesis of MFI zeolite and derived metal-acid bifunctional catalysts for hydroisomerization of n -heptane. J Sol-Gel Sci Techn 112: 348-358. https://doi.org/10.1007/s10971-024-06542-2 Liu BJ, Yang H, Ren LM, Song ZY, Liu QJ, Hou SD, Zhang AF, Guo XW (2025) Rapid synthesis of ZSM-50 zeolites for effective n -heptane hydroisomerization. Chem Mater 37: 6182-6192. https://doi.org/10.1021/acs.chemmater.5c00735 Kang YH, Zhang XQ, Gao J, Liu GH, Li YJ, Gao Y, Bai JJ, Wang AM, Wei XY, Lu CY (2024) Enhanced hydroisomerization of n -heptane over bifunctional catalysts with highly dispersed Pd nanoparticles supported on H-Yβ composite zeolite. Chem Eng J 483. https://doi.org/10.1016/j.cej.2024.149372 Oenema J, Harmel J, Vélez RP, Meijerink MJ, Eijsvogel W, Poursaeidesfahani A, Vlugt TJH, Zečević J, De Jong KP (2020) Influence of nanoscale intimacy and zeolite micropore size on the performance of bifunctional catalysts for n -heptane hydroisomerization. ACS Catal 10: 14245-14257. https://doi.org/10.1021/acscatal.0c03138 Chen HM, Yi FJ, Ma CP, Gao X, Liu SY, Tao ZC, Wu BS, Xiang HW, Yang Y, Li YW (2020) Hydroisomerization of n -heptane on a new kind of bifunctional catalysts with palladium nanoparticles encapsulating inside zeolites. Fuel 268: 117241. https://doi.org/10.1016/j.fuel.2020.117241 Zhu MX, Liu YF, Ma JX, Wang LY, Wang R, Jiang H, Jin CZ (2025) Synthesis of MWW-type zeolite through seed-assisted interzeolite transformation from FAU zeolite. J Sol-Gel Sci Techn 114: 1029-1039. https://doi.org/10.1007/s10971-025-06769-7 Sazama P, Pastvova J, Kaucky D, Moravkova J, Rathousky J, Jakubec I, Sadovska G (2018) Does hierarchical structure affect the shape selectivity of zeolites? Example of transformation of n -hexane in hydroisomerization. J Catal 364: 262-270. https://doi.org/10.1016/j.jcat.2018.05.010 Additional Declarations No competing interests reported. Supplementary Files SupplementaryInformation.docx Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 29 Jan, 2026 Editor assigned by journal 27 Jan, 2026 Submission checks completed at journal 27 Jan, 2026 First submitted to journal 25 Jan, 2026 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8692112","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":582755850,"identity":"3e36e004-5db4-4b80-a33e-25d8fc897acd","order_by":0,"name":"Longyang Wang","email":"","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":false,"prefix":"","firstName":"Longyang","middleName":"","lastName":"Wang","suffix":""},{"id":582755851,"identity":"6f684523-558b-4098-856b-b2b89ceeb6f6","order_by":1,"name":"Zihao Yang","email":"","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":false,"prefix":"","firstName":"Zihao","middleName":"","lastName":"Yang","suffix":""},{"id":582755852,"identity":"e41f3e9f-a1f6-4135-b698-ecae28a634e9","order_by":2,"name":"Xin Wang","email":"","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":false,"prefix":"","firstName":"Xin","middleName":"","lastName":"Wang","suffix":""},{"id":582755853,"identity":"ccdc8b24-a66a-4096-a869-e556762e2458","order_by":3,"name":"Tong Wu","email":"","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":false,"prefix":"","firstName":"Tong","middleName":"","lastName":"Wu","suffix":""},{"id":582755854,"identity":"3e1dffdf-a5d4-4a8d-972f-d9e1c403c775","order_by":4,"name":"Changzi Jin","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAApklEQVRIiWNgGAWjYBACxmYQ0cAgx8befoA0LcZ8PGcSSLGqgSFxnoSDAXGqmdt5DzD83FGX3ibBkMDwo2IbMQ7jS2DsPcOW2ybdeICx58xtYrTwGDAztvHktskcSAAyiNcikc4mkWBAkhaDBNK0MPa2JRi2AQP5IFF+Mew/Y8Dws61OXr69/eCDHxXEaGlgYP8B4xwgrB4I5IlSNQpGwSgYBSMbAAAG2jQuBwZMUQAAAABJRU5ErkJggg==","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":true,"prefix":"","firstName":"Changzi","middleName":"","lastName":"Jin","suffix":""},{"id":582755855,"identity":"1d0081f2-936e-4dae-9b51-9439c4288b59","order_by":5,"name":"Rui Wang","email":"","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":false,"prefix":"","firstName":"Rui","middleName":"","lastName":"Wang","suffix":""},{"id":582755856,"identity":"7c026a3a-d4d7-4988-86e3-b7168ad8e4a9","order_by":6,"name":"Heng Jiang","email":"","orcid":"","institution":"Liaoning Shihua University","correspondingAuthor":false,"prefix":"","firstName":"Heng","middleName":"","lastName":"Jiang","suffix":""}],"badges":[],"createdAt":"2026-01-25 11:39:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8692112/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8692112/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":102061316,"identity":"4dbe905d-c5a1-493e-a077-58263a915581","added_by":"auto","created_at":"2026-02-06 17:01:59","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":18559,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of as-synthesized samples from (a) as-HMS (DDA), (b) ca-HMS (DDA), (c) as-HMS (HDA) and (b) ca-HMS (HDA)\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/0d58eabfe158896dadd087d3.png"},{"id":102061327,"identity":"c764168d-ffdd-4b0c-aa70-68479f77d58c","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":691981,"visible":true,"origin":"","legend":"\u003cp\u003eTEM images of samples from (a) ca-HMS (DDA), (b) as-HMS (DDA), (c) ca-HMS (HDA) and (d) as-HMS (HDA). Inset: greater magnification.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/e7332190c69069f7120b5da8.png"},{"id":102061319,"identity":"41560ef1-ad45-4c81-a698-86d5d6d93ed3","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":42480,"visible":true,"origin":"","legend":"\u003cp\u003eN\u003csub\u003e2\u003c/sub\u003e physical adsorption/desorption isotherms for MFI zeolites from (a) ca-HMS (DDA), (b) ca-HMS (HDA), (c) as-HMS (DDA) and (d) as-HMS (HDA).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/2d754163799d2bade7006e5a.png"},{"id":102061328,"identity":"ed6403e3-4cc7-49e4-b3c3-e9a08ab0c0dc","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":22030,"visible":true,"origin":"","legend":"\u003cp\u003ePore size distribution of synthesized zeolites from (a) as-HMS (DDA), (b) as-HMS (HDA), (c) ca-HMS (DDA) and (d) ca-HMS (HDA).\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/ac225d3d987795c6e88d6b79.png"},{"id":102061317,"identity":"2d0eab6a-0696-4ca3-9d8c-3657e54609ba","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":62185,"visible":true,"origin":"","legend":"\u003cp\u003eRepresentation of synthetic mechanism for hierarchical MFI zeolite.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/a9b41eee18eeefeb0b78af00.png"},{"id":102061321,"identity":"86bf204d-a64a-4a44-8828-6251fb539643","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":19198,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of samples synthesized from (a) as-synthesized MCM-41 and solid silica gel cooperated with (b) CTAB and (c) DDA.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/b7ba8cd4ff4fad4a7fd9973e.png"},{"id":102061323,"identity":"9478f846-1841-4923-ab4e-798a98e14a20","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":630955,"visible":true,"origin":"","legend":"\u003cp\u003eTEM images of bifunctional catalysts based on the zeolites from (a) as-HMS (DDA), (b) ca-HMS (DDA), (c) as-HMS (HDA) and (d) ca-HMS (HDA).\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/761e2817bd6ba694c2d0ef82.png"},{"id":102295886,"identity":"92d1cbbc-494a-46cb-b4b1-9aff4eba74ca","added_by":"auto","created_at":"2026-02-10 10:15:50","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":24613,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of bifunctional catalysts based on the zeolites from (a) as-HMS (DDA), (b) ca-HMS (DDA), (c) as-HMS (HDA) and (d) ca-HMS (HDA).\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/51a338c297a15241f6e64cd2.png"},{"id":102296150,"identity":"641b99f1-8c78-4077-8dbe-5d3a61167a97","added_by":"auto","created_at":"2026-02-10 10:17:45","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":30834,"visible":true,"origin":"","legend":"\u003cp\u003eNH\u003csub\u003e3\u003c/sub\u003e-TPD profiles of synthesized bifunctional catalysts.\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/389ba44a4ebeb57f12e55497.png"},{"id":102061325,"identity":"51a98926-9e46-446e-a669-4ab552727422","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":36305,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003en\u003c/em\u003e-heptane conversion (a) and selectivity for isomerization (b) and cracking (c) over the catalysts with zeolite supports synthesized from (■) as-HMS(DDA), (●) ca-HMS(DDA), (▲) as-HMS(HDA) and (★) ca-HMS(HDA).\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/e6ba8c120c4f0bc18afe123e.png"},{"id":102295757,"identity":"5ad8f1e5-1256-4428-a255-9466eb27280d","added_by":"auto","created_at":"2026-02-10 10:14:43","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":16949,"visible":true,"origin":"","legend":"\u003cp\u003eRatio of multi-branched to total isomer selectivity of different catalysts at 240 \u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/6b411270d928e30ad9335198.png"},{"id":102299122,"identity":"91b6f09d-68b1-4b71-960f-55a04d77844d","added_by":"auto","created_at":"2026-02-10 11:03:08","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2182228,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/0761f5fd-8013-42fd-a8f9-f7f6059bea5b.pdf"},{"id":102061322,"identity":"c0d10438-af5c-49ee-8688-54c2ea3011ec","added_by":"auto","created_at":"2026-02-06 17:02:00","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":293999,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-8692112/v1/643f018ab3b66eb7e04e3a2f.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Sustainable synthesis of hierarchical MFI zeolite from mesoporous HMS and catalytic application","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe crystalline aluminosilicate zeolites are a class of important inorganic materials, which possess abundant porosity, huge surface area, regulable acidity and excellent stability and are widely used in many industrial processes, such as heterogeneous catalysis, adsorption and separation, ion exchange and so on [1\u0026ndash;7]. As typical member of aluminosilicate zeolites, the MFI-type ZSM-5 with 10-ring three-dimensional channel has attracted numerous attentions for its outstanding performance in petrochemical and fine chemicals processing [8\u0026ndash;13]. However, the pore sizes of ZSM-5 and most other aluminosilicate zeolites are usually less than 1.0 nm, which have caused serious diffusional problem, especially in the processes with bulky molecules involved [14]. Therefore, introducing the mesopores or macropores into the microporous zeolites to construct hierarchical matrix has been regarded as one of the most effective strategies to facilitate the mass transfer of the materials [15\u0026ndash;21].\u003c/p\u003e \u003cp\u003eTo date, the researchers have done a large number of research on the preparations of hierarchical zeolites, which can be classified into two protocols of bottom-up and top-down [22, 23]. In the former protocol, the thermally decomposable substances, such as surfactants, polymers or carbon materials are usually added into the synthetic system of zeolites as template (soft- or hard-template) [24\u0026ndash;27]. The hierarchical structure can be formed by removing these templates from the crystallized zeolite products. During this process, effective templates and suitable synthetic technology are crucial to obtain the hierarchical zeolites. The top-down protocol is the post-treatment of microporous zeolites by desilication or dealumination to yield the hierarchical structure [28\u0026ndash;30]. Although no special templates are required in top-down synthesis route, it is not easy to control the dissolution of initial zeolite, as well as the generation of hierarchical porosities. In addition, the loss of zeolite body is inevitable in this top-down process. Therefore, developing more facile and effective synthesis strategies for hierarchical zeolites is still one of the research focuses currently.\u003c/p\u003e \u003cp\u003eIn view of the economic and environmental shortcomings of conventional hydrothermal synthesis of zeolites, the sustainable synthesis method without organic templates or solvents has attracted more and more attentions [31\u0026ndash;36]. Moreover, the green synthesis ideas have also been extended to the fabrication of hierarchical zeolites in recent years [37]. For example, the hierarchical zeolites can be prepared in mesoporogen-free system by finely controlling synthesis condition or appropriate pretreatment to construct porous raw materials [38, 39]. Xiao and co-workers had synthesized hierarchical aluminosilicate and silicoaluminophosphate zeolites via sustainable processes with neither solvent nor mesoporogen, during which the gaseous expansion in crystallization process may be responsible for the formation of mesopores [40]. In addition to the conventional commercial silica and aluminia source, some natural materials such as kaolin, diatomite, rectorite and rice husk ash had also been utilized to synthesize hierarchical zeolites, which are described as sustainable source approach [41\u0026ndash;43]. The sustainable approaches without organic templates or solvents reduce the costs and the noxious pollutants and offer distinct advantages over conventional synthesis processes. However, the generation process of hierarchical structure may be different in various sustainable synthesis approaches. Therefore, it is desired to develop novel efficient sustainable synthesis method for hierarchical zeolites and explore the formation mechanism of hierarchical structure as well.\u003c/p\u003e \u003cp\u003eIn this work, we reported a novel organic template-free and solvent-free sustainable synthesis approach for hierarchical ZSM-5 zeolite with mesoporous silica HMS as silica source. The mesoporous silica source before and after calcination had generated hierarchical zeolite with different porous structure. The long-chain alkylamine occluded in HMS silica source did not hinder the formation of MFI topology and would serve as mesoporogen for hierarchical zeolite product. The hierarchical ZSM-5 was functionalized with Pt sites to construct bifunctional catalysts, which exhibited excellent performance in hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Chemicals\u003c/h2\u003e \u003cp\u003eTetraethylorthosilicate (TEOS), dodecylamine (DDA), hexadecylamine (HDA), and chloroplatinic acid (H\u003csub\u003e2\u003c/sub\u003ePtCl\u003csub\u003e6\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) were purchased from Beijing Innochem Science and Technology Ltd. Ethanol (EtOH), sodium aluminate (NaAlO\u003csub\u003e2\u003c/sub\u003e), sodium hydroxide (NaOH) and ammonium chloride (NH\u003csub\u003e4\u003c/sub\u003eCl) were purchased from Tianjin Damao Chemical Co. Silica gel was purchased from Qingdao Xinchanglai Silica Gel Ltd. All the chemicals were of analytical grade and used as received without any purification. The distilled water was homemade.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of mesoporous HMS\u003c/h2\u003e \u003cp\u003eThe mesoporous silica HMS was prepared according to the published approach with some modification [44]. Typically, 2.40 g DDA (or 3.13 g HDA) was dissolved into 19 mL ethanol, followed by the addition of 31.5 mL water under continuous stirring. Then, 10 g TEOS was added dropwise into the solution and the obtained mixture was further stirred at room temperature for 18 h. The solid product was collected by filtration and dried at 100 \u003csup\u003eo\u003c/sup\u003eC. The as-synthesized HMS (as-HMS) was calcined at 600 \u003csup\u003eo\u003c/sup\u003eC under air atmosphere for 6h to remove the organic components, and the calcined HMS (ca-HMS) can be obtained.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Synthesis of hierarchical ZSM-5\u003c/h2\u003e \u003cp\u003eThe hierarchical ZSM-5 was synthesized through sustainable quasi-solid phase approach in the absence of organic template or abundant solvent [45]. Typically, the mesoporous HMS (as-synthesized or calcined samples), NaAlO\u003csub\u003e2\u003c/sub\u003e, NaOH and H\u003csub\u003e2\u003c/sub\u003eO were mixed together as molar ratio of 1.0SiO\u003csub\u003e2\u003c/sub\u003e : 0.025Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e : 0.072Na\u003csub\u003e2\u003c/sub\u003eO : 2.0H\u003csub\u003e2\u003c/sub\u003eO and grinded for 10 min in agate mortar. The final mixture was transferred into Teflon-lined autoclave and heated at 170 \u003csup\u003eo\u003c/sup\u003eC for 48 h. The products from as-synthesized HMS need to be calcined at 600 \u003csup\u003eo\u003c/sup\u003eC for 6 h to remove the alkylamine. The H-type zeolites were prepared by the ion-exchange of Na-type counterparts with NH\u003csub\u003e4\u003c/sub\u003eCl (1M) aqueous solution at 80 \u003csup\u003eo\u003c/sup\u003eC for 6 h, followed by calcination at 550 \u003csup\u003eo\u003c/sup\u003eC in air for 4 h.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Synthesis of bifunctional catalysts\u003c/h2\u003e \u003cp\u003eThe Pt/ZSM-5 bifunctional catalysts were prepared via incipient-wetness impregnation method with H\u003csub\u003e2\u003c/sub\u003ePtCl\u003csub\u003e6\u003c/sub\u003e as Pt precursor. The theoretical Pt loading of bifunctional catalysts is 0.5%.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Characterization\u003c/h2\u003e \u003cp\u003eSmall and wide-angle X-ray diffraction (XRD) patterns were measured in Bruck D8 Advance powder X-ray diffractometer using Cu Kα radiation. Transmission electronic microscopy (TEM) images were obtained on JEM-2100 electronic microscope with an accelerating voltage of 200 kV. Nitrogen physical adsorption/desorption isotherms were recorded on BSD-660M A6M physical adsorption analyzer. The specific surface areas were calculated using the BET method and the pore size distributions were calculated from the adsorption branches of the isotherms by using NLDFT method. Ammonia temperature programmed desorption (NH\u003csub\u003e3\u003c/sub\u003e-TPD) measurements were performed on Quantachrome TPD/TDR-Pulsar chemisorption analyzer in the range of 150\u0026ndash;600\u0026deg;C at a ramp rate of 20\u0026deg;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The SiO\u003csub\u003e2\u003c/sub\u003e/Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e ratio of the samples was calculated based on the analysis on Bruker D8 Tiger X-ray fluorescence (XRF) spectrometer.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e2.6 Hydroisomerization reaction of \u003cem\u003en\u003c/em\u003e-heptane\u003c/h2\u003e \u003cp\u003eThe hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane were operated on a fixed-bed stainless steel reactor at atmospheric pressure. Before reaction, the Pt/ZSM-5 bifunctional catalysts were treated by H\u003csub\u003e2\u003c/sub\u003e flow at 400\u0026deg;C for 2h, and then was cooled to reaction temperature. The \u003cem\u003en\u003c/em\u003e-heptane was fed into reactor with HPLC pump at a weight hourly space velocity (WHSV) of 2.0 h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and the H\u003csub\u003e2\u003c/sub\u003e was controlled by mass flowmeter to fix the molar ratio of H\u003csub\u003e2\u003c/sub\u003e/\u003cem\u003en\u003c/em\u003e-heptane at 10. The reaction products were on-line analyzed via gas chromatography (Techcomp GC7890) equipped with a TM-PONA capillary column and FID detector.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Synthesis and characterization of hierarchical ZSM-5\u003c/h2\u003e \u003cp\u003eThe sustainable synthesis approach for ZSM-5 zeolites herein is an organotemplate-free quasi-solid phase process by using mesoporous silica (HMS) and NaAlO\u003csub\u003e2\u003c/sub\u003e as silica and aluminum source, respectively. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows the wide-angle XRD patterns of as-synthesized samples. Obviously, all the obtained samples from either as-synthesized or calcined HMS possessing typical MFI topology. Our previous report confirmed the availability of solid silica gel in the synthesis of MFI zeolites without the assistance of OSDA or solvent [45]. Current result indicates that the silica source of mesoporous HMS is also effective in this sustainable synthesis process. Even the alkylamine (DDA or HDA) occluded in the mesopores of HMS did not significantly disrupte the formation of zeolite product. In addition, it should be noted that the obtained zeolites do not exhibit any diffraction signals in small-angle region, which indicates that the ordered mesoporous channel of HMS predecessor had not remained in final zeolite products (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e presents the TEM images of the obtained MFI zeolites from different silica sources. It is interesting that the as-synthesized and calcined HMS generated the zeolite products with different porous structure. For the calcined HMS-derived samples (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea and c), the vesicular mesopores with size of a few nanometers to tens of nanometers can be observed. However, similar porous feature had not been found in the samples from as-synthesized HMS containing alkylamine (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb and d). Different from the synthesis system reported by Xiao\u0026rsquo;s group, where large amounts of NH\u003csub\u003e3\u003c/sub\u003e can be generated by the reaction of Na\u003csub\u003e2\u003c/sub\u003eSiO\u003csub\u003e3\u003c/sub\u003e and NH\u003csub\u003e4\u003c/sub\u003eCl, the starting raw materials herein (HMS, NaAlO\u003csub\u003e2\u003c/sub\u003e and NaOH) will not generate enough gaseous products [40]. Therefore, the formation of mesoporosity in calcined HMS-derived zeolites might be due to other reasons. In fact, our previous report had disclosed the distinct porous structure of MFI zeolites from different silica sources via the solvent-free process [45]. Compared to single microporous product from bulky solid silica gel, the silica nanospheres had yielded hierarchical zeolite, which indicated that the particle size of silica sources may have an impact on the porous structure of final product. Back to current research, the calcined HMS turned into hierarchical zeolite, possibly because the precursors tend to break into small pieces during grinding process compared to as-synthesized ones with alkylamine filling in mesopores. In addition, the alkylamine-removed calcination process may also lead to some of the bulky silica matrix break (Figure S2). During the solvent-free synthesis process, the interspace of tiny particles of silica sources more likely to be reserved and form the mesoporosity of final zeolite products.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIt is worth noting that although the as-synthesized HMS did not generate zeolites with obvious mesoporosity, greater magnification of TEM images indicate that the products possess wormlike porosity (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb and d, inset), which is similar to the HMS predecessor (Figure S2). This phenomenon implies that the alkylamine (DDA or HDA) in the channel of HMS may be involved into zeolite grain during this quasi-solid phase synthesis process. Then, after calcining to remove the organic alkylamine, the zeolite products with additional porosities had been obtained. However, it is inevitable that the mesopores of HMS shrink during the crystallization process, which lead to smaller pores in zeolite products than the amorphous HMS silica source.\u003c/p\u003e \u003cp\u003eThe textural properties of synthesized zeolites were further tested by N\u003csub\u003e2\u003c/sub\u003e physical adsorption measurement. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e presents the isotherms of the obtained samples. Apparently, all the ZSM-5 zeolites show the feature of type-I isotherm with obvious N\u003csub\u003e2\u003c/sub\u003e uptake at low pressure region (P/P\u003csub\u003e0\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.1), which are due to the intrinsic microporous crystallite of zeolite. For the ca-HMS-derived zeolites, the hysteresis can be found at P/P\u003csub\u003e0\u003c/sub\u003e of 0.5\u0026thinsp;~\u0026thinsp;1.0 (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea and b), indicating the presence of additional bigger pores in the samples, which is consistent with the TEM results (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea and c). By comparison, the isotherms of samples from as-HMS are relatively flat at higher pressure region (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec and d). Instead, a weak step at P/P\u003csub\u003e0\u003c/sub\u003e of around 0.1 had been observed, which is due to N\u003csub\u003e2\u003c/sub\u003e filling in the pores with uniform pore size and is similar to type-IV isotherms assigning to mesoporous materials. The pore size distribution of the samples provides more intuitive information. As Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e has shown, the as-HMS-derived zeolites exhibit wide distribution centered around 1.5\u0026thinsp;~\u0026thinsp;1.7 nm, while the samples from ca-HMS do not exhibit any obvious distribution at this region. Therefore, these \u0026ldquo;big micropores\u0026rdquo; in as-HMS-derived zeolites might arise from the mesopores of HMS for the accommodation of alkylamine. However, the pore size of generated \u0026ldquo;big micropores\u0026rdquo; in zeolite products is smaller than the HMS predecessor (Figure S3). Moreover, the HMS-HDA with bigger mesopores did not generate the \u0026ldquo;bigger micropores\u0026rdquo; in final zeolite product. As stated above, the reason is probably that the mesoporous structure of HMS collapsed during crystallization process and lead to the uncontrolled shrinkage of original mesopores. In addition, as Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e has shown, both specific surface area and pore volume of as-HMS-derived zeolites are higher than that of samples generated from ca-HMS, which indicate that these \u0026ldquo;big micropores\u0026rdquo; are more helpful to improve the textural properties of samples.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTextural properties of synthesized zeolites\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSilica source\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e/Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003cp\u003emolar ratio\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSurface area\u003c/p\u003e \u003cp\u003e(m\u003csup\u003e2\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePore volume\u003c/p\u003e \u003cp\u003e(cm\u003csup\u003e3\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eas-HMS-DDA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e59\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e378\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.17\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eca-HMS-DDA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e255\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.15\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eas-HMS-HDA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e398\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.18\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eca-HMS-HDA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e56\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e265\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.14\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eAccording to the results described above, the formation mechanism of hierarchical MFI zeolites from mesoporous HMS can be represented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. For the bulky silica source (such as solid silica gel), the conventional microporous zeolite has been obtained during the quasi-solid phase synthesis. Although the silica sources possess mesoporous structure (Figure S4), the mesoporosity cannot be reserved in final zeolite products without effective supports. When the silica source possesses tiny particles (Stӧber SiO\u003csub\u003e2\u003c/sub\u003e sphere or ca-HMS), the interspaces of particles are likely to evolve into the mesoporosity of final zeolite products, even if the silica source is nonporous. It should be noted that the formation of ca-HMS with tiny particles possesses fortuity and uncontrollability, as well as the corresponding synthesis process for hierarchical zeolite. As to the as-synthesized HMS with alkylamine template in the mesopores, the original mesoporous structure will collapse during crystallization process. Because of the supporting effect of alkylamine, however, the mesoporosity of HMS can be reserved in zeolite product, just shrank to a certain degree.\u003c/p\u003e \u003cp\u003eBased on the experimental results and proposed synthetic mechanism, the feasibility of mesoporous materials, such as MCM-41 with CTAB as template, for synthesis of hierarchical zeolites was also investigated. From the XRD analysis showed in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e, one can find that compared to the HMS, the product with very low MFI topology crystallinity had been generated by using as-synthesized MCM-41 as silica source. The broad signal at 2θ of 18-25\u003csup\u003eo\u003c/sup\u003e is assigned to the amorphous silica, which indicates that CTAB might have negative effect on the OSDA-free quasi-solid phase crystallization process. In order to verify this point, CTAB and DDA were respectively added into the synthetic system with solid silica gel as silica source. Regardless of the availability of solid silica gel for the sustainable synthesis of ZSM-5, the MFI zeolite cannot be obtained with the addition of CTAB (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb). By comparison, the sample from DDA-involved system possesses complete MFI topology, though there is some cristobalite impurity displaying the diffraction peak at 21.7\u003csup\u003eo\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec). Therefore, the alkylamine has lesser impact on the sustainable synthesis of MFI zeolite without OSDA or solvent, which corroborated the feasibility of HMS for fabrication of hierarchical zeolite during this process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Catalytic application of prepared hierarchical zeolites\u003c/h2\u003e \u003cp\u003eThe Pt/zeolite bifunctional catalysts with the prepared hierarchical ZSM-5 as acid support were synthesized through incipient-wetness impregnation method. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e presents the TEM images of the prepared catalysts. It can be found that the Pt particle sizes at different zeolite supports are also different. Although the zeolites from as-HMS possess higher specific surface areas than ca-HMS-derived ones (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), the former-generated catalysts show Pt particle size of 3-15nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea,c), which are bigger than that of latter-involved system (~\u0026thinsp;3nm, Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb,d). Considering same Pt theoretic content (0.5wt%) in all catalysts, the different particle size might be related with the porous structure of zeolite supports. The XRD patterns of the synthesized catalysts is showed in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. Obviously, the catalysts from as-HMS-derived zeolites exhibit a weak diffraction peak at 39.7\u003csup\u003eo\u003c/sup\u003e, which can be indexed to the crystalline plane (111) of cubic platinum crystal (00-001-1190). The catalysts based on ca-HMS-derived zeolites do not show any characteristic Pt-related diffraction peaks (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ec,d), which may be due to their small Pt particle size and in accordance with the TEM results (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e presents the NH\u003csub\u003e3\u003c/sub\u003e-TPD profiles of the synthesized bifunctional catalysts. It can be observed that all the catalysts exhibit the profiles consisting of two desorption peaks centered at 150 \u003csup\u003eo\u003c/sup\u003eC and 400 \u003csup\u003eo\u003c/sup\u003eC, which are ascribed to weak and strong acid sites, respectively. According to the XRF results, the alumina content in the zeolite supports is similar and giving the SiO\u003csub\u003e2\u003c/sub\u003e/Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e molar ratio of 50\u0026thinsp;~\u0026thinsp;59 (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Therefore, it is expectable that all the obtained catalysts possess similar acid properties. However, the different intensity of adsorption peak in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e indicates that there are some differences among the acid amount for synthesized catalysts.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe catalytic performance of the synthesized bifunctional catalysts for the hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane was investigated and the results are showed in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e. It has been found that all the catalysts are inactive at low reaction temperature and exhibit the conversion less than 15% at the temperature lower than 220 \u003csup\u003eo\u003c/sup\u003eC (Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003ea). The activity for all catalysts increased with the rise of reaction temperature. Most catalysts give the conversion of \u003cem\u003en\u003c/em\u003e-heptane higher than 80% when the temperature reaches 280 \u003csup\u003eo\u003c/sup\u003eC. Except the catalyst from as-HMS(HDA)-derived zeolite, the gap among the activity of other catalysts is not too much. The highest activity of as-HMS(HDA)-derived catalyst might be related with its high acid amount (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e). Figure\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003eb and c show the selectivities for C\u003csub\u003e7\u003c/sub\u003e isomers and cracked products over the synthesized catalysts at different temperature. Obviously, with the increase of temperature, the isomers selectivity over most catalysts declined quickly, while the cracked products increased. Especially at high temperature (280 \u003csup\u003eo\u003c/sup\u003eC), the cracked reactions dominate (\u0026gt;\u0026thinsp;95%). It should be noted that all the investigated catalysts exhibit the lower isomers selectivity of less than 50% even at lower reaction temperature, which is different from other reported catalytic system [46\u0026ndash;49]. In fact, our previous reports had already demonstrated the inferior catalytic performance of sustainable synthesized MFI zeolite to that of conventional ones for hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane, even though their textural properties are similar [8, 45]. For the MWW zeolite catalysts, however, this is not the case [50]. So, the influence laws over different zeolite type might be distinct for this hydroisomerization reaction. According to the published literature, many factors are influential for the catalytic performance of zeolite-based catalysts, such as zeolitic topology, specific surface area, porous structure, acidity and metal character. The final catalytic performance of catalysts is the result of integrate all these factors.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eDetailed catalytic results over different catalysts at 240 \u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" morerows=\"1\" nameend=\"c2\" namest=\"c1\" rowspan=\"2\"\u003e \u003cp\u003eCatalytic results\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"5\" nameend=\"c7\" namest=\"c3\"\u003e \u003cp\u003eCatalyst with MFI supports from different silica source\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eas-HMS\u003c/p\u003e \u003cp\u003e(DDA)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eca-HMS\u003c/p\u003e \u003cp\u003e(DDA)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eas-HMS\u003c/p\u003e \u003cp\u003e(HDA)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eca-HMS\u003c/p\u003e \u003cp\u003e(HDA)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eSilica solid gel\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eConversion (%)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e26.74\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e24.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e59.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e39.42\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e7.89\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"6\" rowspan=\"7\"\u003e \u003cp\u003eIsomers selectivity\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2-Methyl Hexane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e9.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e19.14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e7.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e5.61\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e39.23\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3-Methyl Hexane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e8.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e12.22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e9.10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e5.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e18.99\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3-Ethyl Pentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.82\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.84\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.77\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2, 2-Dimethylpentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2, 4-Dimethylpentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.19\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.23\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.29\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.29\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3, 3-Dimethylpentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTotal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e19.49\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e32.45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e17.76\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e11.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e59.34\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"9\" rowspan=\"10\"\u003e \u003cp\u003eCracked\u003c/p\u003e \u003cp\u003eselectivity\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMethane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eEthane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePropane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e30.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e25.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e32.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e34.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e14.45\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eIso-Butane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e38.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e33.77\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e43.29\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e44.89\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e21.03\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eButane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e3.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.45\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4.32\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e3.11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2-Methyl Pentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.29\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.14\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3-Methyl Pentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.18\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.06\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHexane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1.14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTotal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e79.16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e66.14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e81.49\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e87.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e37.85\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"4\" rowspan=\"5\"\u003e \u003cp\u003eOthers\u003c/p\u003e \u003cp\u003eselectivity\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMethyl Cyclohexane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.62\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.03\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eEthyl Cyclopentane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.57\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.17\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eToluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUnkown components\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.59\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTotal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.26\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e2.81\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eDetailed catalytic results for the synthesized catalysts are listed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. In addition, the catalyst based on mono-microporous ZSM-5 from solid silica gel was also compared to further explore the impact of hierarchical structure on the catalytic performance of catalysts. It can be found that the hierarchical catalysts from HMS possess higher activity and exhibit reactant conversion of more than 20% at 240 \u003csup\u003eo\u003c/sup\u003eC. By contrast, the mono-microporous catalyst from solid silica gel shows the conversion as low as 7.89% at same temperature, while a higher isomers selectivity. All the investigated catalysts show similar product types, namely the mono-branched 2-/3-methylhexanes and propane/isobutane dominate the isomers and cracked products, respectively, which is a common characteristic of 10-ring zeolite-based catalyst. There is no significant regularity in the different product selectivities of four hierarchical catalysts. Sazama et al had confirmed that the hierarchical structure had no influence on the shape selectivity of zeolite catalyst for hydroisomerization of hexane and the intrinsic zeolitic channel play decisive role in the formation of isomer products [51]. In current research, however, the hierarchical catalysts had generated higher multi-branched isomers contents than mono-microporous counterpart (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e). In general, the formation of muti-branched isomers (\u0026gt;\u0026thinsp;C\u003csub\u003e6\u003c/sub\u003e) is restricted over 10-ring channel zeolite for spatial confinement. The slightly higher multi-branched isomers products contents of HMS-derived catalysts maybe related with their hierarchical structure, especially the catalysts from as-HMS. These results are also significant to the synthesis of high-performance catalysts for hydroisomerization of linear alkanes.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, MFI zeolite with hierarchical structure was successfully synthesized through sustainable OSDA/solvent-free process with mesoporous HMS as silica source. Both as-synthesized and calcined HMS can generate hierarchical zeolite but the mesoporosity of products and corresponding formation mechanism are different. The alkylamine in the as-synthesized HMS does not only impede the crystallization process, but can be involved in zeolite particles and conduce to the reservation of mesoporosity of HMS. The hierarchical structure of calcined HMS-derived zeolites might be due to the tiny particles of silica source. After modified with Pt metal, the obtained hierarchical bifunctional catalysts showed higher activity but lower isomers selectivity in hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane compared to the mono-microporous counterpart. The higher muti-branched isomers contents over HMS-derived catalysts also verified their hierarchical structure. This work not only develop novel strategy for sustainable synthesis of hierarchical zeolite, but also is instructive to fabricate effective catalysts for hydroisomerization of linear alkanes.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eThis manuscript was written through contributions from all authors. LW, CJ and RW wrote the main manuscript text. LW finished the preparation of zeolites. ZY finished catalytic tests. LW, XW and TW finished the characterization and prepared the figures. HJ participated in the discussion and analysis of experiment results. All authors reviewed the manuscript and approved the final version.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e \u003cp\u003eThis work was financial supported supports by the Talent Scientific Research Fund of LNPU (2020XJJL-016) and the Project of the Educational Department of Liaoning Province (LJ212410148035).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eJae J, Tompsett GA, Foster AJ, Hammond KD, Auerbach SM, Lobo RF, Huber GW (2011) Investigation into the shape selectivity of zeolite catalysts for biomass conversion. J Catal 279: 257-268. https://doi.org/10.1016/j.jcat.2011.01.019\u003c/li\u003e\n\u003cli\u003eRahimi N, Karimzadeh R (2011) Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: A review. Appl Catal A-Gen 398: 1-17. https://doi.org/10.1016/j.apcata.2011.03.009\u003c/li\u003e\n\u003cli\u003eOlsbye U, Svelle S, Bjorgen M, Beato P, Janssens TVW, Joensen F, Bordiga S, Lillerud KP (2012) Conversion of methanol to hydrocarbons: How zeolite cavity and pore size controls product selectivity. Angew Chem Int Ed 51: 5810-5831. https://doi.org/10.1002/anie.201103657\u003c/li\u003e\n\u003cli\u003eDemirci S, Ustaoglu Z, Yilmazer GA, Sahin F, Ba\u0026ccedil; N (2014) Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms. Appl Biochem Biotech 172: 1652-1662. https://doi.org/10.1007/s12010-013-0647-7\u003c/li\u003e\n\u003cli\u003eShwan S, Skoglundh M, Lundegaard LF, Tiruvalam RR, Janssens TVW, Carlsson A, Vennestrom PNR (2015) Solid-state ion-exchange of copper into zeolites facilitated by ammonia at low temperature. ACS Catal 5: 16-19. https://doi.org/10.1021/cs5015139\u003c/li\u003e\n\u003cli\u003eP\u0026eacute;rez-Botella E, Valencia S, Rey F (2022) Zeolites in adsorption processes: state of the art and future prospects. Chem Rev 122: 17647-17695. https://doi.org/10.1021/acs.chemrev.2c00140\u003c/li\u003e\n\u003cli\u003eYue ML, Bu KK, Shen W, Xu HL, Huang Z (2026) Stable Ga-MFI zeolite for propane dehydroaromatization constructed by healing Silanol-defect in framework. J Colloid Inter Sci 708. https://doi.org/10.1016/j.jcis.2025.139807\u003c/li\u003e\n\u003cli\u003eZhu MX, Li HQ, Wang X, Wang LY, Wang R, Jiang H, Jin CZ (2025) Spatial configurational construction of Pt-ZSM-5 bifunctional catalysts for hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane. Catal Surv Asia 29: 155-166. https://doi.org/10.1007/s10563-025-09446-5\u003c/li\u003e\n\u003cli\u003eKandula M, Gutta N, Aytam HP, Perupogu V, Manda K, Akula V (2022) Rice husk ash derived SiO\u003csub\u003e2\u003c/sub\u003e for template free synthesis of H-ZSM-5 support for Ni catalyst: investigation on non-oxidative CH\u003csub\u003e4\u003c/sub\u003e cracking for clean H\u003csub\u003e2\u003c/sub\u003e production. Catal Surv Asia 26: 336-345. https://doi.org/10.1007/s10563-022-09365-9\u003c/li\u003e\n\u003cli\u003eRaghav H, Sah L, Joshi B, Tiwari R, Lama P, Sarkar B, Bal R (2025) Conversion of waste plastic into low-carbon olefins: directly producing C-C light olefins from low-density polyethylene waste using a Cu/ZSM-5 catalyst. Green Chem 27: 15192-15199. https://doi.org/10.1039/d5gc04106f\u003c/li\u003e\n\u003cli\u003eQin WC, Li CY, Fu TJ, Cao RW, Wu XQ, Liu YY, Meng FH, Zhan GW, Li Z (2026) Integrating ZSM-5 catalyst with controllable crystal size on macroporous biomass platform for benzene methylation with CO\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e. Fuel 411: 138011. https://doi.org/10.1016/j.fuel.2025.138011\u003c/li\u003e\n\u003cli\u003eYousefi MR, Rahimi S, Rostamizadeh M (2021) Effective high silica ZSM-5 nanocatalyst including Fe and B promoters for production of high value petrochemicals in plastic upgrading process. J Anal Appl Pyrol 156. https://doi.org/10.1016/j.jaap.2021.105108\u003c/li\u003e\n\u003cli\u003eMohammadparast F, Halladj R, Askari S (2015) The crystal size effect of nano-sized ZSM-5 in the catalytic performance of petrochemical processes: A review. Chem Eng Commun 202: 542-556. https://doi.org/10.1080/00986445.2014.952815\u003c/li\u003e\n\u003cli\u003eLi BC, He Y, Geng R, Shao JB, Wei CL, Qin ZF, Wang JG, Fan WB, Dong M (2025) Progress on enhancing the resistance to deactivation of Zn-containing ZSM-5 catalysts for light hydrocarbon aromatization. Chemcatchem 17. https://doi.org/10.1002/cctc.202500085\u003c/li\u003e\n\u003cli\u003eChen LH, Sun MH, Wang Z, Yang WM, Xie ZK, Su BL (2020) Hierarchically structured zeolites: from design to application. Chem Rev 120: 11194-11294. https://doi.org/10.1021/acs.chemrev.0c00016\u003c/li\u003e\n\u003cli\u003eZhang CS, Lu FX, Zhao JC, Wen S, Sun B, Jiang J (2026) Minute-scale synthesis of hierarchical and nanosized ZSM-5 zeolites with high space-time yields. Chem Eng Sci 321: 122931. https://doi.org/10.1016/j.ces.2025.122931\u003c/li\u003e\n\u003cli\u003eJiang JX, Jorda JL, Yu JH, Baumes LA, Mugnaioli E, Diaz-Cabanas MJ, Kolb U, Corma A (2011) Synthesis and structure determination of the hierarchical meso-microporous zeolite ITQ-43. Science 333: 1131-1134. https://doi.org/10.1126/science.1208652\u003c/li\u003e\n\u003cli\u003ePeng P, Gao XH, Yan ZF, Mintova S (2020) Diffusion and catalyst efficiency in hierarchical zeolite catalysts. Natl Sci Rev 7: 1726-1742. https://doi.org/10.1093/nsr/nwaa184\u003c/li\u003e\n\u003cli\u003eQi S, Liu GZ, Wang JL, Zhang HD, Cheng P (2026) L-histidine-controlled synthesis of hierarchical HZSM-5 zeolite with excellent stability and propylene selectivity for 1-butene catalytic cracking. ChemistrySelect 11. https://doi.org/10.1002/slct.202505457\u003c/li\u003e\n\u003cli\u003eGueudr\u0026eacute; L, Milina M, Mitchell S, P\u0026eacute;rez-Ram\u0026iacute;rez J (2014) Superior mass transfer properties of technical zeolite bodies with hierarchical porosity. Adv Funct Mater 24: 209-219. https://doi.org/10.1002/adfm.201203557\u003c/li\u003e\n\u003cli\u003eZhang JY, Wang H, Qin YC, Song LJ (2021) Progress in characterization strategies mass transfer mechanism of hierarchical zeolite. J Petrochem Univ 34: 1-8. https://doi.org/10.3969/j.issn.1006-396X.2021.04.001\u003c/li\u003e\n\u003cli\u003eBai RS, Song Y, Li Y, Yu JH (2019) Creating hierarchical pores in zeolite catalysts. Trends Chem 1: 601-611. https://doi.org/10.1016/j.trechm.2019.05.010\u003c/li\u003e\n\u003cli\u003eJia XC, Khan W, Wu ZJ, Choi J, Yip ACK (2019) Modern synthesis strategies for hierarchical zeolites: Bottom-up versus top-down strategies. Adv Powder Technol 30: 467-484. https://doi.org/10.1016/j.apt.2018.12.014\u003c/li\u003e\n\u003cli\u003eWang LF, Zhang Z, Yin CY, Shan ZC, Xiao FS (2010) Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic polymers. Micropor Mesopor Mat 131: 58-67. https://doi.org/10.1016/j.micromeso.2009.12.001\u003c/li\u003e\n\u003cli\u003eSong YD, Hua ZL, Zhu Y, Zhou XX, Wu W, Zhang LL, Shi JL (2012) An in situ carbonaceous mesoporous template for the synthesis of hierarchical ZSM-5 zeolites by one-pot steam-assisted crystallization. Chem-Asian J 7: 2772-2776. https://doi.org/10.1002/asia.201200744\u003c/li\u003e\n\u003cli\u003eChoi M, Cho HS, Srivastava R, Venkatesan C, Choi DH, Ryoo R (2006) Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity. Nat Mater 5: 718-723. https://doi.org/10.1038/nmat1705\u003c/li\u003e\n\u003cli\u003eXiao FS, Wang LF, Yin CY, Lin KF, Di Y, Li JX, Xu RR, Su DS, Schlogl R, Yokoi T, Tatsumi T (2006) Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. Angew Chem Int Ed 45: 3090-3093. https://doi.org/10.1002/anie.200600241\u003c/li\u003e\n\u003cli\u003eVerboekend D, P\u0026eacute;rez-Ram\u0026iacute;rez J (2011) Design of hierarchical zeolite catalysts by desilication. Catal Sci Technol 1: 879-890. https://doi.org/10.1039/c1cy00150g\u003c/li\u003e\n\u003cli\u003eZhao LA, Gao JS, Xu CM, Shen BJ (2011) Alkali-treatment of ZSM-5 zeolites with different SiO\u003csub\u003e2\u003c/sub\u003e/Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e ratios and light olefin production by heavy oil cracking. Fuel Process Technol 92: 414-420. https://doi.org/10.1016/j.fuproc.2010.10.003\u003c/li\u003e\n\u003cli\u003eYu LL, Huang SJ, Miao S, Chen FC, Zhang S, Liu ZN, Xie SJ, Xu LY (2015) A facile top-down protocol for postsynthesis modification of hierarchical aluminum-rich mfi zeolites. Chem-Eur J 21: 1048-1054. https://doi.org/10.1002/chem.201404817\u003c/li\u003e\n\u003cli\u003eRen WG, Li J, Han LN, Wang B, Wang JC, Chang LP, Bao WR (2024) One-step synthesis of zeolite ZSM-5 from perlite tailings by crystal seed solution assisted method. Fuel 374. https://doi.org/10.1016/j.fuel.2024.132489\u003c/li\u003e\n\u003cli\u003eJablonska M, Palcic A, Lukman MF, Wach A, Bertmer M, Poppitz D, Denecke R, Wu XC, Simon U, P\u0026ouml;ppl A, Gl\u0026auml;ser R (2023) OSDA-free seeded Cu-containing ZSM-5 applied for NH\u003csub\u003e4\u003c/sub\u003e-SCR-DeNO\u003csub\u003ex\u003c/sub\u003e. ACS Omega 8: 41107-41119. https://doi.org/10.1021/acsomega.3c03721\u003c/li\u003e\n\u003cli\u003eLiu P, Wu QM, Yan KP, Wang L, Xiao FS (2022) Solvent-free synthesis of FAU zeolite from coal fly ash. Dalton T 52: 24-28. https://doi.org/10.1039/d2dt03196e\u003c/li\u003e\n\u003cli\u003eYin HT, Wang W, Li YX, Wen H, Chen S, Jiang NZ (2024) An eco-friendly method for the scale-up synthesis of ZSM-5 Zeolite. Micropor Mesopor Mat 365. https://doi.org/10.1016/j.micromeso.2023.112907\u003c/li\u003e\n\u003cli\u003eJin YY, Sun Q, Qi GD, Yang CG, Xu J, Chen F, Meng XJ, Deng F, Xiao FS (2013) Solvent-free synthesis of silicoaluminophosphate zeolites. Angew Chem Int Ed 52: 9172-9175. https://doi.org/10.1002/anie.201302672\u003c/li\u003e\n\u003cli\u003eDeng LF, Lou CY, Wu QM, Liu XL, Niu J, Du XH, Xu ST, Wang L, Liu ZM, Yu JH, Xiao FS (2025) Insights into the wastewater-free synthesis of zeolites. J Am Chem Soc 147: 42901-42908. https://doi.org/10.1021/jacs.5c15625\u003c/li\u003e\n\u003cli\u003eMaghfirah A, Ilmi MM, Fajar ATN, Kadja GTM (2020) A review on the green synthesis of hierarchically porous zeolite. Mater Today Chem 17. https://doi.org/10.1016/j.mtchem.2020.100348\u003c/li\u003e\n\u003cli\u003eYue YY, Gu LL, Zhou YN, Liu HY, Yuan P, Zhu HB, Bai ZS, Bao XJ (2017) Template-free synthesis and catalytic applications of microporous and hierarchical ZSM-5 zeolites from natural aluminosilicate minerals. Ind Eng Chem Res 56: 10069-10077. https://doi.org/10.1021/acs.iecr.7b02531\u003c/li\u003e\n\u003cli\u003eKadja GTM, Mukti RR, Liu ZD, Rilyanti M, Ismunandar, Marsih IN, Ogura M, Wakihara T, Okubo T (2016) Mesoporogen-free synthesis of hierarchically porous ZSM-5 below 100 \u0026deg;C. Micropor Mesopor Mat 226: 344-352. https://doi.org/10.1016/j.micromeso.2016.02.007\u003c/li\u003e\n\u003cli\u003eZhang CS, Wu QM, Lei C, Pan SX, Bian CQ, Wang L, Meng XJ, Xiao FS (2017) Solvent-free and mesoporogen-free synthesis of mesoporous aluminosilicate ZSM-5 zeolites with superior catalytic properties in the methanol-to-olefins reaction. Ind Eng Chem Res 56: 1450-1460. https://doi.org/10.1021/acs.iecr.7b00062\u003c/li\u003e\n\u003cli\u003eAlaba PA, Sani YM, Daud WMaW (2015) Synthesis and characterization of hierarchical nanoporous HY zeolites from acid-activated kaolin. Chin. J. Catal. 36: 1846-1851. https://doi.org/10.1016/S1872-2067(15)60962-7\u003c/li\u003e\n\u003cli\u003eZhang CQ, Li SQ, Bao SC (2018) A facile and green method for the synthesis of hierarchical ZSM-5 zeolite aggregates from rice husk ash. Research on Chemical Intermediates 44: 3581-3595. https://doi.org/10.1007/s11164-018-3326-z\u003c/li\u003e\n\u003cli\u003eHartanto D, Kurniawati R, Pambudi AB, Utomo WP, Leaw WL, Nur H (2019) One-pot non-template synthesis of hierarchical ZSM-5 from kaolin source. Solid State Sci 87: 150-154. https://doi.org/10.1016/j.solidstatesciences.2018.11.015\u003c/li\u003e\n\u003cli\u003eLi SY, Huang B, Jin CZ, Wang R, Jiang H, Yang GS, Huang SJ (2023) Selective conversion of ethanol and acetaldehyde to 1,3-butadiene over Zr-HMS catalysts. Catal Surv Asia 27: 207-216. https://doi.org/10.1007/s10563-023-09390-2\u003c/li\u003e\n\u003cli\u003eZhu MX, Xu WQ, Wang LY, Wang R, Jiang H, Jin CZ (2024) Sustainable synthesis of MFI zeolite and derived metal-acid bifunctional catalysts for hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane. J Sol-Gel Sci Techn 112: 348-358. https://doi.org/10.1007/s10971-024-06542-2\u003c/li\u003e\n\u003cli\u003eLiu BJ, Yang H, Ren LM, Song ZY, Liu QJ, Hou SD, Zhang AF, Guo XW (2025) Rapid synthesis of ZSM-50 zeolites for effective \u003cem\u003en\u003c/em\u003e-heptane hydroisomerization. Chem Mater 37: 6182-6192. https://doi.org/10.1021/acs.chemmater.5c00735\u003c/li\u003e\n\u003cli\u003eKang YH, Zhang XQ, Gao J, Liu GH, Li YJ, Gao Y, Bai JJ, Wang AM, Wei XY, Lu CY (2024) Enhanced hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane over bifunctional catalysts with highly dispersed Pd nanoparticles supported on H-Y\u0026beta; composite zeolite. Chem Eng J 483. https://doi.org/10.1016/j.cej.2024.149372\u003c/li\u003e\n\u003cli\u003eOenema J, Harmel J, V\u0026eacute;lez RP, Meijerink MJ, Eijsvogel W, Poursaeidesfahani A, Vlugt TJH, Zečević J, De Jong KP (2020) Influence of nanoscale intimacy and zeolite micropore size on the performance of bifunctional catalysts for \u003cem\u003en\u003c/em\u003e-heptane hydroisomerization. ACS Catal 10: 14245-14257. https://doi.org/10.1021/acscatal.0c03138\u003c/li\u003e\n\u003cli\u003eChen HM, Yi FJ, Ma CP, Gao X, Liu SY, Tao ZC, Wu BS, Xiang HW, Yang Y, Li YW (2020) Hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane on a new kind of bifunctional catalysts with palladium nanoparticles encapsulating inside zeolites. Fuel 268: 117241. https://doi.org/10.1016/j.fuel.2020.117241\u003c/li\u003e\n\u003cli\u003eZhu MX, Liu YF, Ma JX, Wang LY, Wang R, Jiang H, Jin CZ (2025) Synthesis of MWW-type zeolite through seed-assisted interzeolite transformation from FAU zeolite. J Sol-Gel Sci Techn 114: 1029-1039. https://doi.org/10.1007/s10971-025-06769-7\u003c/li\u003e\n\u003cli\u003eSazama P, Pastvova J, Kaucky D, Moravkova J, Rathousky J, Jakubec I, Sadovska G (2018) Does hierarchical structure affect the shape selectivity of zeolites? Example of transformation of \u003cem\u003en\u003c/em\u003e-hexane in hydroisomerization. J Catal 364: 262-270. https://doi.org/10.1016/j.jcat.2018.05.010\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"catalysis-surveys-from-asia","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cats","sideBox":"Learn more about [Catalysis Surveys from Asia](http://link.springer.com/journal/10563)","snPcode":"10563","submissionUrl":"https://submission.nature.com/new-submission/10563/3","title":"Catalysis Surveys from Asia","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Hierarchical, MFI zeolite, HMS, Sustainable synthesis, Hydroisomerization","lastPublishedDoi":"10.21203/rs.3.rs-8692112/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8692112/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eConstructing hierarchical structure in conventional zeolites is a promising means to overcome intrinsic shortcomings of this type of microporous material. In this research, a novel synthesis strategy for hierarchical zeolite was presented. By utilizing mesoporous HMS as silica source, MFI aluminosilicate with mesoporosity was successfully prepared through sustainable process without organic template or large amounts of solvent. The obtained products were characterized by a series of techniques, including X-ray diffraction, transmission electronic microscopy, N\u003csub\u003e2\u003c/sub\u003e physical adsorption, X-ray fluorescence and NH\u003csub\u003e3\u003c/sub\u003e temperature programmed desorption. It has been shown that as-synthesized and calcined HMS had generated MFI zeolite with different mesoporosity, based on which the different synthesis mechanisms for hierarchical products were proposed. The alkylamine dose not impede the sustainable synthesis of MFI zeolite, which endow the availability of HMS for green synthesis of hierarchical zeolite. After loaded with platinum, the obtained hierarchical bifunctional catalysts show higher activity but lower isomers selectivity in hydroisomerization of \u003cem\u003en\u003c/em\u003e-heptane compared to mono-microporous counterpart. In addition, the mesoporosity of the catalysts had led to the higher multi-branched isomers productivity.\u003c/p\u003e","manuscriptTitle":"Sustainable synthesis of hierarchical MFI zeolite from mesoporous HMS and catalytic application","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-06 17:01:55","doi":"10.21203/rs.3.rs-8692112/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-01-30T02:19:30+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-01-27T06:30:48+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-01-27T06:26:46+00:00","index":"","fulltext":""},{"type":"submitted","content":"Catalysis Surveys from Asia","date":"2026-01-25T11:24:04+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"catalysis-surveys-from-asia","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cats","sideBox":"Learn more about [Catalysis Surveys from Asia](http://link.springer.com/journal/10563)","snPcode":"10563","submissionUrl":"https://submission.nature.com/new-submission/10563/3","title":"Catalysis Surveys from Asia","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"6aa97383-79ea-4926-b458-56934578370f","owner":[],"postedDate":"February 6th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-04-30T00:53:21+00:00","versionOfRecord":[],"versionCreatedAt":"2026-02-06 17:01:55","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8692112","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8692112","identity":"rs-8692112","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}