ChemCatChem最新文献_第8页

Advances and Perspectives of Mild Thermal Treatment Strategy in Covalent/Metal-Organic Frameworks Derived Porous Catalysts 共价/金属-有机骨架衍生多孔催化剂温和热处理策略的研究进展与展望

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-27 DOI: 10.1002/cctc.202401981

Jinyan Wang, Huimin Sun, Yu Wu, Hailong Hu, Fang Duan, Mingliang Du, Shuanglong Lu

{"title":"Advances and Perspectives of Mild Thermal Treatment Strategy in Covalent/Metal-Organic Frameworks Derived Porous Catalysts","authors":"Jinyan Wang, Huimin Sun, Yu Wu, Hailong Hu, Fang Duan, Mingliang Du, Shuanglong Lu","doi":"10.1002/cctc.202401981","DOIUrl":"10.1002/cctc.202401981","url":null,"abstract":"Mild thermal treatment (MTT) strategy is an emerging method for designing covalent/metal-organic frameworks (COFs/MOFs) derived porous catalysts, which can not only maintain their unique porous and periodic structures but also endow them with new properties. This review systematically examines the recent advancements in deriving materials from COFs/MOFs via MTT strategy. The discussion encompasses various types of derivatives, including framework-carbon composites, framework-metal nanoparticle hybrids, and mesoporous structures. These materials demonstrate notable advantages in catalysis, such as enhanced electrical conductivity, improved structural stability, and the incorporation of abundant active sites, which collectively contribute to their superior catalytic performance. Furthermore, we critically analyze the structural and functional enhancements enabled by these derivatives, emphasizing their contributions to advancing catalytic applications. In addition, we propose future research directions, including elucidating the mechanisms underlying material transformations during thermal treatment, diversifying catalyst design strategies, and establishing precise structure–performance relationships. These insights aim to provide a comprehensive understanding of the interplay between catalyst structures and their functionalities, thereby guiding the rational design of next-generation catalytic materials.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135738","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

Sustainable Strategies for Fixation of CO2 into Valuable Chemicals Catalyzed by Functionalized Porous Materials 功能化多孔材料催化二氧化碳转化为有价化学品的可持续策略

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-27 DOI: 10.1002/cctc.202500807

Dr. Debarati Chakraborty, Dr. Arindam Modak, Prof. Asim Bhaumik

{"title":"Sustainable Strategies for Fixation of CO2 into Valuable Chemicals Catalyzed by Functionalized Porous Materials","authors":"Dr. Debarati Chakraborty, Dr. Arindam Modak, Prof. Asim Bhaumik","doi":"10.1002/cctc.202500807","DOIUrl":"10.1002/cctc.202500807","url":null,"abstract":"Bulk scale utilization of CO2 as C1 feedstock is very demanding not only from the environmental perspective, but it is very challenging for addressing the global energy crisis, carbon recycling, and sustainability. Functionalized porous materials having CO2 adsorption sites and large internal surface areas are the ideal candidates for catalyzing the fixation of CO2 into fuels and commodity chemicals. In this review we have highlighted the advancements made in designing different class of microporous and mesoporous materials (zeolites, mesoporous materials, MOFs, COFs, POPs, metal phosphonates, etc.) over the years for the synthesis of cyclic carbonates, polycarbonates, carbamates, N-formylated amines, polyhydroxyurethanes, ureas, imidazoles, and related heterocyclic compounds through CO2 fixation reactions. Further, direct CO2 reduction to methanol, dimethyl ether (DME), formic acid, ethanol, etc. are particularly important in the context of renewable energy. We have discussed the catalytic role of different class of porous nanomaterials for understanding the promotional role of the reactive sites in catalyzing these CO2 conversion reactions. Mechanistic aspects of these chemical transformations are illustrated with a major emphasis on the key factors affecting the CO2 and substrate activation processes. Finally, the challenges faced by the researchers in achieving the desired targets in these CO2 conversion reactions are highlighted, which could contribute significantly in carbon recycling in the future.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144999117","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

Structure and Reactivity of AgCu/SiO2 Bimetallic Catalysts for Alkene Epoxidation 烯烃环氧化AgCu/SiO2双金属催化剂的结构和反应性

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-27 DOI: 10.1002/cctc.202500921

Yogita Soni, Seth March, Steven L. Suib, E. Charles H. Sykes, Prashant Deshlahra

{"title":"Structure and Reactivity of AgCu/SiO2 Bimetallic Catalysts for Alkene Epoxidation","authors":"Yogita Soni, Seth March, Steven L. Suib, E. Charles H. Sykes, Prashant Deshlahra","doi":"10.1002/cctc.202500921","DOIUrl":"10.1002/cctc.202500921","url":null,"abstract":"AgCu bimetallic materials have attracted significant interest as catalysts for selective oxidation reactions. Near-surface alloys of Ag on Cu have been shown to activate O2 efficiently at exposed reverse-segregated isolated Cu atoms within the surface Ag layers. This study focuses on the synthesis of nanoparticle analogs of these alloys and measurement of their performance for ethylene and propylene epoxidation. Supported Cu/SiO2 catalysts were prepared by strong electrostatic adsorption and partial galvanic replacement of Cu atoms with Ag cations in aqueous media, which led to bimetallic nanoparticles of 3–10 nm average size and 0.25–1.6 Ag:Cu atomic ratios. Galvanic exchange stoichiometry, elemental maps and UV–vis spectroscopy reveal coexistence of Ag and Cu in the nanoparticles. Diffuse reflectance infrared spectra of bound CO indicate the formation of nanoparticles with a Cu core and Ag shell when catalysts with high Ag:Cu ratios are reduced to metallic form. The bimetallic catalysts show improvement over monometallic Ag and Cu and their physical mixtures, exhibiting higher rates, higher initial selectivity than Ag, and resistance to secondary reactions that decrease the selectivity of Cu catalysts at higher alkene conversion. These results demonstrate a simple synthesis method of more selective bimetallic AgCu nanoparticles with core-shell like structures, which may be of use in a variety of selective oxidation reactions.","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":"145102360","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

H2O2 Suppression During Oxygen Reduction Using Mixed Metal Oxides 混合金属氧化物对氧还原过程中H2O2的抑制作用

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-07-27 DOI: 10.1002/cctc.202500886

Sekhar Kumar Biswal, Chinmoy Ranjan

{"title":"H2O2 Suppression During Oxygen Reduction Using Mixed Metal Oxides","authors":"Sekhar Kumar Biswal, Chinmoy Ranjan","doi":"10.1002/cctc.202500886","DOIUrl":"10.1002/cctc.202500886","url":null,"abstract":"The development of efficient and selective oxygen reduction reaction (ORR) catalysts is central to advancing electrochemical energy technologies. While platinum remains the benchmark, its high cost, peroxide selectivity, and durability issues demand alternatives. Transition metal oxides (TMOs) are promising in alkaline media, yet their ORR activity is hampered by weak oxygen binding and high activation barriers. This concept article introduces a coordination mismatch strategy to enhance ORR performance in mixed-metal oxides, specifically Cu[M]Ox (M═Co, Ni, Fe, Mn). By combining metals with differing oxygen coordination preferences, Cu2+ (four-fold) and Mn+ (typically six-fold), local lattice strain and undercoordinated sites are introduced, enhancing O2 adsorption and O─O bond cleavage. Cu-rich compositions, especially Cu0.8Co0.2Ox/Au, demonstrate high ORR activity, low H2O2 yield, and excellent stability. In situ Raman spectroscopy confirms stable M─O─Cu frameworks and redox-active Cu centers. The approach is validated across multiple dopants and supported by DFT studies showing stabilized OOH* intermediates and favorable energetics. These findings demonstrate that coordination engineering is a powerful strategy for designing efficient, selective, and robust nonprecious metal catalysts for electrochemical energy conversion.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135737","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

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