{"title":"Chemoenzymatic Polymerization/Depolymerization of Semiaromatic Polyamides for Chemical Recycling","authors":"Kousuke Tsuchiya, Hiroyasu Masunaga, Keiji Numata","doi":"10.1021/acssuschemeng.4c09489","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09489","url":null,"abstract":"Chemical recycling of polymeric materials represents a promising approach for achieving sustainable material cycles, yet conventional chemical recycling based on depolymerization methods often requires harsh conditions and is limited in the narrow scope of available polymers. In this study, novel semiaromatic polyamides consisting of 4-amino-3-hydroxybenzoic acid (Ahb) and peptide moieties were enzymatically synthesized by papain-catalyzed polymerization in aqueous media. The monomer sequence significantly affected polymerizability, with GlyAhbGly, AlaAhbGly, and SerAhbGly sequences successfully yielding their corresponding polyamides under mild enzymatic conditions. Wide angle X-ray diffraction analysis revealed that the periodic sequences determined the crystalline structures of the polyamides, indicating that selecting appropriate amino acid residues can tune their physical properties. All the polyamides showed enzymatic degradation behavior in aqueous protease solutions, and particularly those with AlaAhbGly and SerAhbGly sequences underwent sequence-selective degradation into their corresponding monomer units when treated with proteinase K. The mild enzymatic polymerization and depolymerization of the semiaromatic polyamides will offer a chemical recycling approach for polyamide materials that are difficult to break down into monomers through a conventional thermal process.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"210 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Edita Jasiukaitytė-Grojzdek*, Tina Ročnik Kozmelj, Giorgio Tofani, Britt Segers, Philippe Nimmegeers, Pieter Billen, Rok Pogorevc, Blaž Likozar and Miha Grilc,
{"title":"Design of Organosolv Lignin Fractionation: Influence of Temperature, Antisolvent, and Source on Molecular Weight, Structure, and Functionality of Lignin Fragments","authors":"Edita Jasiukaitytė-Grojzdek*, Tina Ročnik Kozmelj, Giorgio Tofani, Britt Segers, Philippe Nimmegeers, Pieter Billen, Rok Pogorevc, Blaž Likozar and Miha Grilc, ","doi":"10.1021/acssuschemeng.4c0812510.1021/acssuschemeng.4c08125","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08125https://doi.org/10.1021/acssuschemeng.4c08125","url":null,"abstract":"<p >Lignin offers a sustainable alternative to fossil raw materials for chemical and material synthesis. Improving its utilization requires the production of lignin fragments with a controlled dispersity and reactivity. In this study, a sustainable protocol for direct organosolv lignin fractionation from black liquor using water as an antisolvent is developed. The approach utilizes the complementarity of the process temperature and solubility parameters to generate lignin streams with tailored properties. In particular, the protocol allows control of the structural characteristics of the lignin fractions, including OH group content, interunit bonds, and degree of ethoxylation, as demonstrated for spruce and beech lignins. The ability to adjust the ratio of aliphatic to aromatic OH groups emphasizes the potential to significantly influence the reactivity and functionality of the lignin. This water-driven fractional precipitation approach offers a sustainable way to produce well-defined lignin streams suitable for various applications, depending on the desired properties. In addition, a techno-economic assessment highlights solvent recovery and lignin value as key parameters for scaling up the process and highlights both opportunities and challenges in implementing this process on an industrial scale.</p><p >Fractionation in combination with other parameters (process temperature, solubility, wood type) produces well-defined lignin fractions for various applications.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 9","pages":"3452–3466 3452–3466"},"PeriodicalIF":7.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acssuschemeng.4c08125","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143576616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kousuke Tsuchiya*, Hiroyasu Masunaga and Keiji Numata,
{"title":"Chemoenzymatic Polymerization/Depolymerization of Semiaromatic Polyamides for Chemical Recycling","authors":"Kousuke Tsuchiya*, Hiroyasu Masunaga and Keiji Numata, ","doi":"10.1021/acssuschemeng.4c0948910.1021/acssuschemeng.4c09489","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09489https://doi.org/10.1021/acssuschemeng.4c09489","url":null,"abstract":"<p >Chemical recycling of polymeric materials represents a promising approach for achieving sustainable material cycles, yet conventional chemical recycling based on depolymerization methods often requires harsh conditions and is limited in the narrow scope of available polymers. In this study, novel semiaromatic polyamides consisting of 4-amino-3-hydroxybenzoic acid (Ahb) and peptide moieties were enzymatically synthesized by papain-catalyzed polymerization in aqueous media. The monomer sequence significantly affected polymerizability, with GlyAhbGly, AlaAhbGly, and SerAhbGly sequences successfully yielding their corresponding polyamides under mild enzymatic conditions. Wide angle X-ray diffraction analysis revealed that the periodic sequences determined the crystalline structures of the polyamides, indicating that selecting appropriate amino acid residues can tune their physical properties. All the polyamides showed enzymatic degradation behavior in aqueous protease solutions, and particularly those with AlaAhbGly and SerAhbGly sequences underwent sequence-selective degradation into their corresponding monomer units when treated with proteinase K. The mild enzymatic polymerization and depolymerization of the semiaromatic polyamides will offer a chemical recycling approach for polyamide materials that are difficult to break down into monomers through a conventional thermal process.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 10","pages":"3994–4004 3994–4004"},"PeriodicalIF":7.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631566","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Binghua Ye, Cheng Liu, Yueling Chen, Qi Chen, Kaiqiang Jing, Jimmy C. Yu, Jionghua Wu* and Ling Wu*,
{"title":"Regulating the Unsaturated Co Sites on MOF-74(Co) for Enhancing Photocatalytic N2 to NH3 Conversion","authors":"Binghua Ye, Cheng Liu, Yueling Chen, Qi Chen, Kaiqiang Jing, Jimmy C. Yu, Jionghua Wu* and Ling Wu*, ","doi":"10.1021/acssuschemeng.4c0965310.1021/acssuschemeng.4c09653","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09653https://doi.org/10.1021/acssuschemeng.4c09653","url":null,"abstract":"<p >Photocatalytic N<sub>2</sub> fixation is a green and sustainable pathway for the synthesis of ammonia. However, its efficiency is considerably restricted by the energy-intensive activation of N<sub>2</sub> molecules. Herein, a series of MOF-74(Co) with varying contents of coordinatively unsaturated Co sites were synthesized through the thermal treatment at different temperatures (<i>T</i> = 100, 150, 200, 250 °C). These photocatalysts were used for the photocatalytic fixation of N<sub>2</sub> in the absence of a sacrificial agent. The experimental results and theoretical computations indicate that the amount of coordinatively unsaturated Co sites increases as the temperature elevates by the removal of coordinated H<sub>2</sub>O from MOF-74(Co). These Co sites can function as active sites to promote chemisorption and activation of N<sub>2</sub> molecules. The sample MOF-74(Co)-200 exhibits the highest NH<sub>4</sub><sup>+</sup> production rate of 84 μmol·g<sup>–1</sup>·h<sup>–1</sup>, which is six times higher than that of the pristine MOF-74(Co) (13.9 μmol·g<sup>–1</sup>·h<sup>–1</sup>). The enhanced performance can be ascribed to the abundance of active sites and the optimal mobility of the photogenerated charges. Finally, a mechanism is proposed for the photocatalytic N<sub>2</sub> activation at the molecular level.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 9","pages":"3588–3599 3588–3599"},"PeriodicalIF":7.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143576553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chen Ling, Ryan W. Clarke, Gloria Rosetto, Shu Xu, Robin M. Cywar, Dong Hyun Kim, Levi J. Hamernik, Stefan J. Haugen, William E. Michener, Sean P. Woodworth, Torrey M. Lind, Kelsey J. Ramirez, Meltem Urgun-Demirtas, Davinia Salvachúa, Christopher W. Johnson, Nicholas A. Rorrer* and Gregg T. Beckham*,
{"title":"Tunable and Degradable Dynamic Thermosets from Compatibilized Polyhydroxyalkanoate Blends","authors":"Chen Ling, Ryan W. Clarke, Gloria Rosetto, Shu Xu, Robin M. Cywar, Dong Hyun Kim, Levi J. Hamernik, Stefan J. Haugen, William E. Michener, Sean P. Woodworth, Torrey M. Lind, Kelsey J. Ramirez, Meltem Urgun-Demirtas, Davinia Salvachúa, Christopher W. Johnson, Nicholas A. Rorrer* and Gregg T. Beckham*, ","doi":"10.1021/acssuschemeng.5c0094310.1021/acssuschemeng.5c00943","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00943https://doi.org/10.1021/acssuschemeng.5c00943","url":null,"abstract":"<p >Polyhydroxyalkanoates (PHAs) are versatile, biobased polyesters that are often targeted for use as degradable thermoplastic replacements for polyolefins. Given the substantial chemical diversity of PHA, their potential as cross-linked polymers could also enable similar platforms for reversible, degradable thermosets. In this work, we genetically engineered <i>Pseudomonas putida</i> KT2440 to synthesize poly(3-hydroxybutyrate-<i>co</i>-3-hydroxyundecenoate) (PHBU), which contains both 3-hydroxybutyrate and unsaturated 3-hydroxyundecenoate components. To reduce the brittleness of this polymer, we physically blended PHBU with the soft copolymer poly(3-hydroxydecanonate-<i>co</i>-3-hydroxyundecenoate) in mass ratios of 1:3, 1:1, and 3:1. Upon observing varying degrees of immiscibility by scanning electron microscopy, we installed dynamic boronic ester cross-links via thiol–ene click chemistry, which resulted in compatibilized dynamic thermoset blends ranging in hard, medium, and soft rubber or elastomer thermomechanical profiles. These dynamic thermoset blends were subjected to controlled biological degradation experiments in freshwater conditions, achieving timely mass loss despite the cross-linked architectures. Overall, this work highlights a two-component platform for the production of degradable and reprocessable dynamic thermoset blends suitable for several classes of cross-linked polymer technologies from tailored, biological PHA copolymers.</p><p >Microbially produced polymers are cross-linked to form rubber-like materials. These biobased materials can be reprocessed and are biodegradable.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 9","pages":"3817–3829 3817–3829"},"PeriodicalIF":7.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acssuschemeng.5c00943","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143576562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Highly Shear-Thickening Electrolyte with Impact Resistance for Flexible Aqueous Zinc-Ion Batteries","authors":"Lijie Luo, Ling Jiang, Qi Song, Qing Chen, Wenjie Huang, Zhiquan Hu, Hongming Chen, Shuo Huang* and Yongjun Chen*, ","doi":"10.1021/acssuschemeng.4c0997910.1021/acssuschemeng.4c09979","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09979https://doi.org/10.1021/acssuschemeng.4c09979","url":null,"abstract":"<p >Aqueous zinc-ion batteries (ZIBs) are desirable for large-scale energy storage due to their high energy density, cost-effectiveness, and eco-friendliness. However, the enhancement of their durability under impact remains a major challenge since traditional liquid electrolytes are prone to leakage when subjected to severe shocks or impacts. In this study, a novel shear-thickening electrolyte was reported by integrating starch with Zn(CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub> electrolyte. Under normal conditions, this electrolyte behaves like a conventional liquid electrolyte with excellent ionic conductivity, low viscosity, and high fluidity. While upon exposure to external force stimuli, the liquid electrolyte can change to a solid. Moreover, the starch molecules have strong interactions with Zn<sup>2+</sup>, promoting the epitaxial electroplating of Zn on the anode and effectively suppressing dendrite formation. The ZIBs fabricated based on this shear-thickening electrolyte possess good electrochemical performance and stability, with a capacity retention rate of 96.5% after 3000 cycles at 2 A g<sup>–1</sup>. More interestingly, the assembled AlVO/CC-50%/Zn flexible battery demonstrates high capacity retention after bending at angles of up to 90°. This shear- thickening electrolyte prevents the battery from damage caused by external force, thereby significantly boosting the impact resistance and the flexible properties of ZIBs.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 9","pages":"3660–3668 3660–3668"},"PeriodicalIF":7.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143576625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dun Li, Heming Dong, Guoqiang Song, Qian Du, Sibudjing Kawi, Jianmin Gao
{"title":"Hydrogen and Carbon Nanofiber Coproduction by Methane Decomposition over Ni/Diatomite Catalysts","authors":"Dun Li, Heming Dong, Guoqiang Song, Qian Du, Sibudjing Kawi, Jianmin Gao","doi":"10.1021/acssuschemeng.4c09321","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09321","url":null,"abstract":"Catalytic decomposition of methane (CDM) is a unique potential technology, producing only CO<sub><i>x</i></sub>-free hydrogen and solid carbon. Reducing the cost of catalysts and finding application scenarios for the large amount of carbon byproducts are unavoidable issues in the CDM application process. Therefore, natural diatomite materials, which are abundant and environmentally friendly, were used as catalyst support in this paper. Nickel phyllosilicates were synthesized on the surface of diatomite by a hydrothermal method, and well-dispersed Ni/diatomite catalysts were obtained by high-temperature reduction. The maximum methane conversion of the catalyst was 30% at 500 °C, and the CNFs were uniformly adhered to the diatomite support surface. Both metal loading and temperature could affect hydrogen yield and structural characterization of CNFs. Theoretically, this CNFs/diatomite composite can be added to natural rubber as a filler and enhance its heat dissipation properties. In addition, no CO<sub>2</sub> production was detected during the reaction. Our results provide new insights into the preparation of catalysts and carbon production application of CDM, which can further improve the economics of CDM.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"51 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143506842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cornelis Post, Paul van den Tempel, Paula Herrera Sánchez, Dina Maniar, Ranjita K. Bose, Vincent S. D. Voet, Rudy Folkersma, Francesco Picchioni, Katja Loos
{"title":"Thermoreversible Diels–Alder Cross-Linking of BHMF-Based Polyesters: Synthesis, Characterization and Rheology","authors":"Cornelis Post, Paul van den Tempel, Paula Herrera Sánchez, Dina Maniar, Ranjita K. Bose, Vincent S. D. Voet, Rudy Folkersma, Francesco Picchioni, Katja Loos","doi":"10.1021/acssuschemeng.4c09338","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09338","url":null,"abstract":"2,5-Bis(hydroxymethyl)furan (BHMF)-based polyesters are an interesting new class of biobased and potentially biodegradable furanic polymers. However, their thermal properties are currently insufficient, making them unsuitable for potential applications as commodity plastics. To improve this, several polyesters were synthesized using an enzymatic bulk polymerization process with the monomers BHMF and aliphatic dimethyl esters of varying spacer lengths. The BHMF units were subsequently cross-linked with a biobased bismaleimide (BM-689) through a [4 + 2] cycloaddition reaction between the furan and maleimide groups. This approach clearly demonstrated that these furan-based polyesters can be thermoreversibly cross-linked using this bismaleimide. The use of different spacer lengths further allows the variation in relative reaction rates and affects the reversibility and reprocessability of the polymers. In situ <sup>1</sup>H NMR spectroscopy revealed the identification of the endo- and exostereoadducts formed by the Diels–Alder reaction. A rheological analysis demonstrated the reprocessability and the thermal properties were further characterized via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). This study sheds light on the thermal and mechanical enhancement of biobased BHMF-based polyesters, while maintaining their recyclability, which widens the range of potential application of this promising polymer.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jianguo Shi, Xiaofeng Song, Feng Wang, Juanfen Chen, Yanhe Wang, Xingyun Wang, Ye Liu
{"title":"Phosphorus- and Nitrogen-Bridged Chitooligosaccharide as an Effective Flame-Retardant Coating of Fiber Cardboard","authors":"Jianguo Shi, Xiaofeng Song, Feng Wang, Juanfen Chen, Yanhe Wang, Xingyun Wang, Ye Liu","doi":"10.1021/acssuschemeng.4c07464","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07464","url":null,"abstract":"Fiber cardboard as one type of plant fiberboard is often used as a package and building material; however, its intrinsic flammability throws up big obstacles to its wide application. In this work, a phosphorus- and nitrogen-bridged chitooligosaccharide (CPDF) is synthesized via a two-step substitution method. The CPDF can be well dissolved in alcohol solvents and coated on the surface of the fiber cardboard. With increasing coating rate, the flame retardation efficiency and bending resistance of fiber cardboard increase. Because the coating rate is 21.7 wt %, the fiber cardboard exhibits outstanding fire safety, of which its limiting oxygen index is 28% and its UL-94 rating is B-1 grade. The peak heat release rate (PHRR), total heat release (THR), and average effective heat release (Av-EHR) decreased correspondingly. The inflaming retarding mechanism was put forward. A seed layer is produced initially to retard heat exchange and lower the damage to the internal polymer matrix; subsequently, phosphorus–oxygen radical dequenching as well as noncombustible gas dilution and a ripe carbon layer barrier cross each other, “braking” the “fire-car” completely. CPDF coating enhances the bending resistance of fiber cardboard, and stiffness climbed from 1124.8 to 1198.5 mN·m. Even after undergoing durability tests, CPDF retains its good inflammable retarding ability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"69 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143506841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tao Zheng, Tianli Hui*, Haiyan Liu*, Rui Zhang, Xianghai Meng, Zhichang Liu and Chunming Xu,
{"title":"Direct Organotemplate-Free Synthesis of Nanorod-Assembled Mordenite: Nucleation-Inducing Mechanism of Activated Natural Aluminosilicate Minerals","authors":"Tao Zheng, Tianli Hui*, Haiyan Liu*, Rui Zhang, Xianghai Meng, Zhichang Liu and Chunming Xu, ","doi":"10.1021/acssuschemeng.4c1004310.1021/acssuschemeng.4c10043","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10043https://doi.org/10.1021/acssuschemeng.4c10043","url":null,"abstract":"<p >Nanosized hierarchical zeolites, combining the advantages of both nanoscale crystal and hierarchical pore structure, exhibited superior catalytic performance due to their shorter diffusion paths, reduced mass resistance, and more accessible active sites. Here, different from the traditional synthesis methods that create nanocrystals by using crystal growth modifiers, inhibitors, and/or zeolite seeds, we report a sustainable and simple method, characterized by kinetically modulated crystallization, for synthesizing nanosized hierarchical mordenite (HR-MOR) from quasi-solid-phase activated kaolin (QSP-kaolin) and thermally activated diatomite (TAD). Benefiting from the self-assembled nucleation-inducing property of QSP-kaolin and the progressive dissolution characteristics of TAD, a nanorod-assembled HR-MOR was synthesized neither using any Al- and Si-containing chemical reagents nor involving any growth modifier and organic structure-directing agents (OSDAs). Compared to conventional mordenite, the HR-MOR has a larger external surface area, enhanced acid site accessibility, and framework Fe species, which endows it with the superior catalytic performance in benzylation reaction of benzene with benzyl alcohol. Our work provides a sustainable and low-cost alternative for the direct synthesis of nanosized zeolites, entirely eliminating the need for Al- and Si-based chemical reagents, zeolite seeds, growth modifiers, and OSDAs.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 9","pages":"3669–3684 3669–3684"},"PeriodicalIF":7.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143576609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}