ChemCatChem最新文献_第3页

Functional Integration of [Ir(ppy)₂(H2dcbpy)] and a Molecular Nickel Complex into Metal-Organic Frameworks for Photocatalytic CO2 Reduction [Ir(ppy) 2 (H2dcbpy)]和分子镍配合物在光催化CO2还原金属-有机框架中的功能集成

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-27 DOI: 10.1002/cctc.202500844

Osman Ali, Aruntima Das, Anupam Jana, Sinjini Mandal, Ashadul Adalder, Dr. Bholanath Maity, Dr. Asamanjoy Bhunia

{"title":"Functional Integration of [Ir(ppy)₂(H2dcbpy)] and a Molecular Nickel Complex into Metal-Organic Frameworks for Photocatalytic CO2 Reduction","authors":"Osman Ali, Aruntima Das, Anupam Jana, Sinjini Mandal, Ashadul Adalder, Dr. Bholanath Maity, Dr. Asamanjoy Bhunia","doi":"10.1002/cctc.202500844","DOIUrl":"10.1002/cctc.202500844","url":null,"abstract":"Developing multifunctional photocatalysts that efficiently convert CO₂ into valuable chemical products (e.g., CO, CH4, HCOOH, and CH3OH) is essential for achieving sustainable development. To address this challenge, we report a remarkable multifunctional metal-organic framework (MOF)-based photocatalyst, termed UiO-67-Ni-Ir, which has been elegantly crafted through an in situ synthesis strategy. This promising catalyst contains a highly efficient light-absorbing iridium unit, [Ir(ppy)₂(H2dcbpy)] (where ppy = 2-phenylpyridine, H2dcbpy = 2,2′-bipyridine-4,4′-dicarboxylic acid), referred to as Ir-PS, in conjunction with a catalytically active nickel center. The broad absorption of visible light of the Ir-PS unit empowers the efficient CO2 reduction reactions under visible light illumination. The photocatalyst UiO-67-Ni-Ir exhibits exceptional photocatalytic performance, producing 5800 µmol g−1 of formate (HCOO⁻) over a 6 h period with a remarkable selectivity of 96.5%. This high formate yield is further supported by a turnover number (TON) exceeding 51 during the same photocatalysis run, which is ten times higher than that of the corresponding homogeneous system. Moreover, this catalyst is completely heterogeneous and recyclable, making it an attractive candidate for the photocatalytic conversion of CO2 to formate under visible light irradiation. Furthermore, a plausible mechanism has been proposed based on the photophysical and electrochemical study along with density functional theory (DFT), which provides a comprehensive understanding of the underlying catalytic process.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photocatalytic Selective Anaerobic Oxidation of 5-Hydroxymethylfurfural via Zn0.5Cd0.5S/NaBiS2 S-Scheme Heterojunction Zn0.5Cd0.5S/NaBiS2 S-Scheme异质结光催化选择性厌氧氧化5-羟甲基糠醛

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-24 DOI: 10.1002/cctc.202500804

Shuanglong Li, Donghui Wang, Jiaxu Chen, Haiyang Zhang, Feng Chen

{"title":"Photocatalytic Selective Anaerobic Oxidation of 5-Hydroxymethylfurfural via Zn0.5Cd0.5S/NaBiS2 S-Scheme Heterojunction","authors":"Shuanglong Li, Donghui Wang, Jiaxu Chen, Haiyang Zhang, Feng Chen","doi":"10.1002/cctc.202500804","DOIUrl":"10.1002/cctc.202500804","url":null,"abstract":"Photocatalytic conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to the high-value-added chemical 2,5-diformylfuran (DFF) coupled with concurrent hydrogen production offers an efficient and sustainable strategy for simultaneously obtaining green energy and fine chemicals. In this study, a series of Zn0.5Cd0.5S/NaBiS2 (ZCS/NBS) composites featuring S-type heterojunctions were successfully prepared via a one-step alkaline hydrothermal method, achieving efficient photocatalytic anaerobic oxidation of HMF to selectively produce DFF while co-producing H2. HRTEM observation confirms the formation of a tightly integrated heterojunction between the ZCS and NBS. An interfacial electric field formed at the heterojunction of ZCS/NBS significantly enhances the migration and separation efficiency of photogenerated carriers. Under visible-light irradiation, the ZCS/NBS-7 composite exhibits superior photocatalytic performance, achieving an HMF conversion of 67.81% with a DFF selectivity of 95.69%. This HMF conversion is 5.4 times higher than that of pristine ZCS (12.46%), while the H2 production rate reaches 81.11 µmol/g/h, which is 14.4 times greater than that of pristine ZCS (5.63 µmol/g/h). This study highlights the significant application potential of twinned ZCS in the photocatalytic selective anaerobic oxidation of HMF and offers valuable insights into the design of suitable heterojunction materials for photocatalytic organic conversion.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Additive-Free Synthesis of Cyclic Carbamates From Aziridines and CO2 Catalyzed by IER Supported Iron(III) Halides 负载铁（III）卤化物催化氮丙啶和CO2无添加剂合成环氨基甲酸酯

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-24 DOI: 10.1002/cctc.202500710

Matteo Alberti, Marta Gianelli, Djihed Boucherabine, Sandro Recchia, Alessandro Caselli

{"title":"Additive-Free Synthesis of Cyclic Carbamates From Aziridines and CO2 Catalyzed by IER Supported Iron(III) Halides","authors":"Matteo Alberti, Marta Gianelli, Djihed Boucherabine, Sandro Recchia, Alessandro Caselli","doi":"10.1002/cctc.202500710","DOIUrl":"10.1002/cctc.202500710","url":null,"abstract":"The coupling of CO2 with aziridines offers an efficient, 100% atom-economic route to synthesize high-value cyclic carbamates. In this study, we present a heterogeneous catalytic system based on readily available iron(III) metallates supported on commercially available ion-exchange resins (IERs) for the selective synthesis of 1,3-oxazolidin-2-ones. Two polystyrene-based IERs with different porosities, Amberlyst™ 26-Cl (A26-Cl, macroreticular) and Amberlite™ IRA-400-Cl (IRA400-Cl, microporous) were evaluated. The results reveal a synergistic interaction between the iron metallate and the resin support, with the A26-[FeCl3Br] catalyst outperforming the homogeneous counterpart under mild conditions (25 °C, CO2 pressure = 0.8 MPa, 2 h), achieving up to >99% yield of the target oxazolidinone. A Design of Experiments (DoE) approach was applied to optimize reaction parameters, and the system's versatility was confirmed using aziridines with different substitution patterns. Overall, this work presents a scalable (up to 1 g) and cost-effective method for CO2 valorization into cyclic carbamates, highlighting experimentally the combined effect of polystyrene supports and ammonium ferrate active species.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500710","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Carbon-Quantum-Dot-Mediated Z-Scheme Charge Transfer in Vertically Aligned CuBi2O4/CuO Photocathodes for Enhanced Hydrogen Evolution 垂直排列CuBi2O4/CuO光电阴极中碳量子点介导的Z-Scheme电荷转移增强析氢

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-24 DOI: 10.1002/cctc.202500905

Dr. Qinglong Wang, Jingxin Jia, Dr. Jinfeng Liu, Prof. Jianjun Yang

{"title":"Carbon-Quantum-Dot-Mediated Z-Scheme Charge Transfer in Vertically Aligned CuBi2O4/CuO Photocathodes for Enhanced Hydrogen Evolution","authors":"Dr. Qinglong Wang, Jingxin Jia, Dr. Jinfeng Liu, Prof. Jianjun Yang","doi":"10.1002/cctc.202500905","DOIUrl":"10.1002/cctc.202500905","url":null,"abstract":"Photoelectrochemical water splitting represents a pivotal technology for sustainable hydrogen generation; however, its practical application remains constrained by limitations in visible-light utilization efficiency and suboptimal charge carrier management. Here, we rationally designed a Z-scheme heterostructure photocathode featuring hierarchical CuBi2O4@carbon quantum dots (CQDs)/CuO core-shell nanosheet arrays. The vertically aligned CuBi2O4/CuO nanoarchitecture provides a high surface area and directional charge transfer. Strategic integration of CQDs as electron mediators shifts charge transfer from type-II to Z-scheme mechanisms, preserving strong reduction potential for hydrogen evolution while enhancing spatial charge separation. This configuration achieves broad-spectrum light-harvesting capability through complementary bandgap alignment and dramatically enhanced interfacial charge transfer kinetics. The optimized photocathode demonstrates a photocurrent density of −0.95 mA cm−2 at 0.4 V versus RHE under AM 1.5 G irradiation in neutral electrolyte, representing a 6.3-fold and 38-fold increase over pristine CuBi2O4 arrays and disordered CuBi2O4 thin-film counterparts. Notably, the heterojunction system exhibits remarkable charge transfer kinetics due to the CQDs-mediated charge transport pathways. This work establishes an interfacial engineering strategy for developing effective Z-scheme photocathodes, offering critical insights into the rational design of solar-driven hydrogen evolution from water splitting architectures.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Palladium-Catalyzed Telomerization of Isoprene with Amines: Ligands and Solvents Working Together to Improve the Selectivity 钯催化异戊二烯与胺的端粒化：配体和溶剂共同作用以提高选择性

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-24 DOI: 10.1002/cctc.202500786

Dr. Jordi Colavida, Ricardo G. Penido, Ana Collado, Prof. Josep M. Ricart, Dr. Cyril Godard, Prof. Carmen Claver, Prof. Jorge J. Carbó, Prof. Eduardo N. dos Santos, Prof. Sergio Castillon

{"title":"Palladium-Catalyzed Telomerization of Isoprene with Amines: Ligands and Solvents Working Together to Improve the Selectivity","authors":"Dr. Jordi Colavida, Ricardo G. Penido, Ana Collado, Prof. Josep M. Ricart, Dr. Cyril Godard, Prof. Carmen Claver, Prof. Jorge J. Carbó, Prof. Eduardo N. dos Santos, Prof. Sergio Castillon","doi":"10.1002/cctc.202500786","DOIUrl":"10.1002/cctc.202500786","url":null,"abstract":"Controlling the selectivity in palladium-catalyzed telomerization of nonsymmetric dienes represents a challenge as several isomers can be obtained, although the four resulting from the attack of the nucleophile at the terminal carbon atom are the main products. Concerning telomerization of isoprene using amines as nucleophiles, the selectivity for three of these four isomers, tail-to-head, head-to-head, and tail-to-tail (1–3), were previously optimized as a result of solvent (pKa) and ligand control. However, the head-to-tail telomer (4) was always obtained in low selectivity. In this paper, we test different Pd catalytic systems with phosphine, phosphite, and phosphoramidite ligands under different solvents and pKa conditions to improve the selectivity for telomers 3 and 4. Results showed that, in the telomerization of isoprene with diethyl amine using non-protic solvents and phosphite ligands with large cone angle afforded telomer 3 in high yield and selectivity (up to 90% yield and 90% selectivity for 3). Phosphite ligands with small cone angle provided telomer 4 with selectivity of 43% (80% yield), which was raised to 48% (23% yield) with iPr2NH as nucleophile. The significant effect of residual water on the solvent was quantitatively accessed, and greener solvents were tested as alternative for this reaction.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500786","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhanced Activity of Proton-Responsive Protic-NHC-Ru(II) Bis(pincer) Complexes for Electrochemical Water Oxidation 质子响应型质子- nhc - ru (II) - Bis（螯）配合物在电化学水氧化中的活性增强

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-24 DOI: 10.1002/cctc.202501003

Ekta Yadav, Shambhu Nath, Nida Shahid, Achena Saha, Biswanath Das, Amrendra K. Singh

{"title":"Enhanced Activity of Proton-Responsive Protic-NHC-Ru(II) Bis(pincer) Complexes for Electrochemical Water Oxidation","authors":"Ekta Yadav, Shambhu Nath, Nida Shahid, Achena Saha, Biswanath Das, Amrendra K. Singh","doi":"10.1002/cctc.202501003","DOIUrl":"10.1002/cctc.202501003","url":null,"abstract":"A series of homoleptic ruthenium(II)-bis(pincer) complexes (Ru1-4) featuring unsymmetrical CNN pincer ligands are synthesized and characterized using spectroscopic and single-crystal X-ray diffraction techniques. Investigation of these complexes for catalytic electrochemical water oxidation reveals complexes Ru1 and Ru3, with proton-responsive protic-NHC ligands having β-NH functionalities, demonstrate better water oxidation performance compared to their classical-NHC counterparts, Ru2 and Ru4, respectively. Cyclic voltammetry at low temperatures (−30 °C) was conducted to gain insights into the potential active intermediates. The foot of the wave analysis (FOWA) was used to elucidate the operating reaction mechanism, revealing a water nucleophilic attack (WNA) mechanism. Catalytic Tafel plots are employed to evaluate the performance and for benchmarking the catalyst. The Ru1 complex is found to be the most efficient catalyst, among all four complexes in this study, at a modest overpotential (̴ 330 mV vs NHE) with an impressive TON value of 1.6 × 105 over a period of 8 h, giving TOF of 5.53 s−1. Even at a lower overpotential of 140 mV vs NHE, the TON (62560) for Ru1 outperforms most of the homogeneous Ru-systems, other than the Ru(bda) family of complexes, reported so far for the electrochemical water oxidation.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Organo-Soluble MoS₂ Quantum Dots Mediated Photocatalytic Generation of Imminium Intermediate for Effective Synthesis of Bis(indolyl)Methanes Derivatives 有机可溶性MoS 2量子点介导光催化合成双（吲哚基）甲烷衍生物的最小中间体

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-20 DOI: 10.1002/cctc.202500977

Abir Kayal, Mrinmoy De

{"title":"Organo-Soluble MoS₂ Quantum Dots Mediated Photocatalytic Generation of Imminium Intermediate for Effective Synthesis of Bis(indolyl)Methanes Derivatives","authors":"Abir Kayal, Mrinmoy De","doi":"10.1002/cctc.202500977","DOIUrl":"10.1002/cctc.202500977","url":null,"abstract":"Iminium intermediates play a pivotal role in the synthesis of diverse organic molecules due to their exceptional reactivity and capacity to participate in a wide range of transformative reactions. However, their inherent instability in aqueous media, commonly employed in nanomaterial-based catalysis presents a significant challenge. Even though there are few reports of organo-soluble nanophotocatalysis, it has never been explored for iminium ion-mediated pharmaceutically important bis(indolyl)methanes (BIMs) synthesis. In this study, we report the use of organo-soluble MoS₂ quantum dots (QDs) as photocatalysts for the in situ generation of stable iminium ions, which serve as key intermediates in the synthesis of bis(indolyl)methanes (BIMs). Leveraging the unique electronic properties and high surface area of MoS₂ QDs, we achieve efficient substrate activation under mild, environmentally benign conditions, eliminating the need for harsh reagents or elevated temperatures. The in situ generated iminium ions undergo nucleophilic attack by indoles, affording bisindoline derivatives, structural motifs commonly found in biologically active natural products and pharmaceutical agents. Our findings highlight the potential of MoS₂ QDs as sustainable and versatile photocatalysts in organic synthesis, offering a novel and efficient strategy for constructing bisindoline frameworks. This approach not only advances synthetic methodologies but also opens new avenues for the design of catalytic systems aimed at accelerating the discovery of therapeutic agents and bioactive molecules.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanical Understanding of the Roles of Crystal Facets and the Aqueous Solution for the Hydrogenation of LGO to Cyrene with the Pd/Pt Catalysts Pd/Pt催化剂催化LGO加氢制昔烯过程中晶面和水溶液作用的力学理解

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-20 DOI: 10.1002/cctc.202500889

Han-xian Meng, Hao-ze Chen, Bin Hu, Ji Liu, Yang-wen Wu, Kai Li, Yao-bing Huang, Qiang Lu

{"title":"Mechanical Understanding of the Roles of Crystal Facets and the Aqueous Solution for the Hydrogenation of LGO to Cyrene with the Pd/Pt Catalysts","authors":"Han-xian Meng, Hao-ze Chen, Bin Hu, Ji Liu, Yang-wen Wu, Kai Li, Yao-bing Huang, Qiang Lu","doi":"10.1002/cctc.202500889","DOIUrl":"10.1002/cctc.202500889","url":null,"abstract":"Hydrogenation of biomass-derived levoglucosenone (LGO) into versatile dihydroleveglucosenone (Cyrene) is one of the most attractive biomass transformations due to its widespread application in chemical synthesis. LGO hydrogenation is commonly catalyzed by Pd/Pt catalysts, with the reaction being influenced by their crystal facets and reaction environment. Regrettably, the current understanding of the hydrogenation mechanism of LGO to Cyrene over these catalysts is limited. Herein, the catalytic hydrogenation mechanism of LGO to Cyrene on Pd/Pt catalysts was systematically studied based on the first principle calculations. Particularly, the roles of exposed crystal facets and the aqueous solution have been discussed. The hydrogenation of LGO begins with the absorption of its C═C bond, and the optimal pathways over Pd/Pt catalysts vary depending on different crystal facets. In addition, Pd(101) exhibits superior catalytic activity for LGO hydrogenation than that of Pt(111) when comparing the optimal facets of Pb and Pt catalysts (19.50 versus 185.05 kJ mol⁻¹). H2O chiefly affects the hydrogenation reactions by forming a hydrated derivative with LGO, altering the hydrogenation pathway for Cyrene production. This work can provide a theoretical basis for developing high-performance catalysts and exploring new ways to realize the efficient hydrogenation of LGO to Cyrene.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metallogels as Functional Catalysts: Bridging Soft Materials with Sustainable Transformations 金属凝胶作为功能催化剂：桥接软材料与可持续转变

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-20 DOI: 10.1002/cctc.202500640

Sumit Mondal, Joydeep Ray, Debajit Sarma

引用次数: 0

Sulfonic Acid-Functionalized KIT-6 Solid Acid Catalysts for Glycerol Acetylation 磺酸功能化KIT-6固体酸催化剂的甘油乙酰化研究

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-20 DOI: 10.1002/cctc.202500808

Nattha Baingam, Li-Yu Wang, Dr. Shih-Yuan Chen, Fitrah Hardhana, Dr. Chung-Kai Chang, Dr. Hiroyuki Tateno, Dr. Takehisa Mochizuki, Prof. Chia-Min Yang, Prof. Apanee Luengnaruemitchai

{"title":"Sulfonic Acid-Functionalized KIT-6 Solid Acid Catalysts for Glycerol Acetylation","authors":"Nattha Baingam, Li-Yu Wang, Dr. Shih-Yuan Chen, Fitrah Hardhana, Dr. Chung-Kai Chang, Dr. Hiroyuki Tateno, Dr. Takehisa Mochizuki, Prof. Chia-Min Yang, Prof. Apanee Luengnaruemitchai","doi":"10.1002/cctc.202500808","DOIUrl":"10.1002/cctc.202500808","url":null,"abstract":"Blending biodiesel fuel (BDF) with petrodiesel effectively reduces CO₂ emissions in the transportation sector. The carbon footprint can be further minimized by converting crude glycerol, a byproduct of the BDF industry, into high-value products like triacetin, which can serve as a biofuel additive. This study demonstrated the acetylation of glycerol with acetic acid using propylsulfonic acid-functionalized KIT-6 mesoporous silica (PA-KIT-6) as a solid catalyst to produce triacetin. A series of PA-KIT-6 catalysts was synthesized by post-synthesis (grafting) and direct-synthesis (co-condensation) methods with varying sulfonic acid loading, using 3-mercaptopropyltrimethoxysilane (MPTMS) and hydrogen peroxide as precursor and oxidant. In-situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray photoelectron spectra confirm that all catalysts contained Brønsted acid sites, which increased with sulfonic acid loading. The P-20PA-KIT-6 catalyst, with 0.25 mmol g⁻¹ sulfonic acid loading, exhibited the best performance. Glycerol was rapidly consumed, and 52% selectivity for triacetin was achieved using a 1:9 glycerol-to-acetic acid molar ratio and 2.83 wt.% catalyst at 115 °C for 8 h. This catalyst was reusable, maintaining its activity and selectivity over four cycles. This study highlights the intrinsic activity of sulfonic acid-based solid acids with Brønsted acidity in glycerol acetylation, effectively producing triacetin.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500808","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0