ChemCatChem最新文献_第5页

Kinetic Modeling of the Ru-MACHO-Catalyzed CO2 Hydrogenation to Methanol ru - macho催化CO2加氢制甲醇的动力学模型

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202500883

Mohamed E. A. Safy, Raquel J. Rama, Niklas F. Both, Kathrin Junge, Matthias Beller, Ainara Nova

{"title":"Kinetic Modeling of the Ru-MACHO-Catalyzed CO2 Hydrogenation to Methanol","authors":"Mohamed E. A. Safy, Raquel J. Rama, Niklas F. Both, Kathrin Junge, Matthias Beller, Ainara Nova","doi":"10.1002/cctc.202500883","DOIUrl":"https://doi.org/10.1002/cctc.202500883","url":null,"abstract":"One of the most efficient and extensively studied homogeneous catalysts for CO2 hydrogenation to methanol is the Ru-MACHO-Ph complex. However, the exact nature of the resting states of the catalyst, which could be Ru-formate, Ru-carbamate, and [Ru-CO]⁺, as well as the contribution of various pathways for amide hydrogenation, remain unresolved questions. In this study, we employed a computational protocol including conformational search with a semiempirical method (GFN2-xTB), followed by geometry optimization and energy calculations using density functional theory (M06/M06L) and coupled-cluster (DLPNO-CCSD(T)) methods to investigate the most plausible pathways for the CO2 hydrogenation reaction assisted by dimethylamine (DMA). Microkinetic modeling was used to predict the methanol turnover number (TON), which aligns well with experimental data, and to analyze the proposed mechanisms and resting states of the catalyst. Our model indicates that dimethylformamide (DMF) is initially hydrogenated to hemiaminal through a metal-ligand cooperative mechanism. The resulting hemiaminal is then decomposed via a methanol-assisted organic reaction in a catalyst-independent process. Additionally, Ru-formate (3) was identified as the primary resting state, along with Ru-carbamate (8). Furthermore, we found that increasing the DMA concentration enhances the methanol TON, in agreement with previous experimental results.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237395","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

Microwave-Assisted Oxidation of Glucose Using H2O2 and Au/CePO4 Catalysts: A Comparative Study of Gold Deposition Methods and Analysis of Reaction Pathways 微波辅助H2O2和Au/CePO4氧化葡萄糖：沉积金方法的比较研究及反应途径分析

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202500867

Joanna Wisniewska, Izabela Sobczak, Mariusz Pietrowski, Hanna Wywrocka, Michal Mazur, Lukasz Wolski

{"title":"Microwave-Assisted Oxidation of Glucose Using H2O2 and Au/CePO4 Catalysts: A Comparative Study of Gold Deposition Methods and Analysis of Reaction Pathways","authors":"Joanna Wisniewska, Izabela Sobczak, Mariusz Pietrowski, Hanna Wywrocka, Michal Mazur, Lukasz Wolski","doi":"10.1002/cctc.202500867","DOIUrl":"https://doi.org/10.1002/cctc.202500867","url":null,"abstract":"This study aligns with microwave-assisted selective oxidation processes using H2O2 as an environmentally relevant oxidant over heterogeneous gold-based catalysts. The research is focused on assessing the influence of the gold deposition method on the surface properties and catalytic behavior of Au/CePO4 catalysts in the selective oxidation of glucose. A significant part of the study involved also unraveling the nature of active sites and species involved in the oxidation process. For this purpose, three gold deposition methods were applied for the synthesis of Au/CePO4 catalysts, namely deposition–reduction (DR), deposition–precipitation with urea (DPU), and anchoring of gold species on functionalized support (grafting; GR). Au/CePO4-GR was found to significantly outperform the other two materials in terms of H2O2 decomposition efficiency and glucose oxidation. This catalyst enabled highly efficient glucose conversion to gluconic acid in a short reaction time (90% glucose conversion in 20 min, at 120 °C) and could be successfully reused without any significant deactivation. The observed enhancement in the reactivity of Au/CePO4-GR was attributed to its strong surface acidity and the smallest size of gold particles. Furthermore, Au/CePO4-GR exhibited approximately 1.5 times higher activity in glucose oxidation than commercial Au/TiO2 (Mintek), despite its lower efficiency in H2O2 decomposition.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237398","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

Selectivity and Microkinetic Insights on Ethylene Oligomerization over Ni Encapsulated in a Brønsted-less Hollow ZSM-5 Zeolite 无硼空心ZSM-5沸石包覆镍的乙烯低聚选择性和微动力学研究

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202500957

Omar Abed, Hend Omar Mohammed, Rushana Khairova, Idoia Hita, Vijay Velisoju, Natalia Morlanés, Mark Meijerink, Abdul-Hamid Emwas, Sergio Vernuccio, Pedro Castaño

{"title":"Selectivity and Microkinetic Insights on Ethylene Oligomerization over Ni Encapsulated in a Brønsted-less Hollow ZSM-5 Zeolite","authors":"Omar Abed, Hend Omar Mohammed, Rushana Khairova, Idoia Hita, Vijay Velisoju, Natalia Morlanés, Mark Meijerink, Abdul-Hamid Emwas, Sergio Vernuccio, Pedro Castaño","doi":"10.1002/cctc.202500957","DOIUrl":"10.1002/cctc.202500957","url":null,"abstract":"We encapsulated Ni nanoparticles in a hollow ZSM-5 zeolite catalyst using the dissolution-recrystallization method to catalyze ethylene oligomerization. Our aim is to engineer an idealized catalyst free of Brønsted acid contributions to kinetics or deactivation, having isolated and encapsulated Ni2⁺–zeolite species, to study the intrinsic oligomerization kinetics on Ni2⁺–zeolite through an experimental and microkinetic standpoint. We proved how the hollow architecture encapsulates both Ni2⁺ and NiO species, being the former significantly more active and selective toward dimerization. A comprehensive microkinetic model, grounded in the Cossee-Arlman mechanism and parameterized using experimental data, provides a detailed understanding of the reaction network on isolated Ni2⁺ sites. The model reveals that while linear butene formation dominates, its selectivity decreases with increasing ethylene conversion, temperature, and pressure, highlighting the contribution of isomerization pathways at elevated temperatures. This study focuses on the method to develop isolated oligomerization sites and then studies the intrinsic microkinetic pathways and rates.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145101053","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

Non-Noyori-Type Ruthenium-POP Pincer Catalysts in Ethanol Upgrading 非noyori型钌- pop钳形催化剂在乙醇精制中的应用

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202500700

Alexander T. Nikol, Rosa Padilla, Martin Nielsen

引用次数: 0

Catalytic Methods for Purification of Exhaust Gases Produced by Ammonia-Fueled Engines 氨燃料发动机废气净化的催化方法

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202500768

Prof.Dr. Lucjan Chmielarz

引用次数: 0

Front Cover: In Situ Elucidation of Reaction Mechanisms in Electrocatalysis Using Scanning Electrochemical Microscopy (ChemCatChem 15/2025) 封面：使用扫描电化学显微镜原位阐明电催化反应机理（ChemCatChem 15/2025）

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-07 DOI: 10.1002/cctc.70238

Jaxiry S. Barroso-Martínez, María Escudero-Escribano

引用次数: 0

Cover Feature: Mono- and Dimetallic [Mn(CO)3] Complexes with the Iminopyridine Ligand for Both Hydrogen and Syngas Productions (ChemCatChem 15/2025) 封面特征：与亚氨基吡啶配体的单金属和双金属[Mn(CO)3]配合物用于氢气和合成气生产（ChemCatChem 15/2025）

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-07 DOI: 10.1002/cctc.70239

Vera V. Khrizanforova, Robert R. Fayzullin, Ruslan B. Zaripov, Tatiana P. Gerasimova, Vladimir I. Morozov, Evgeniya B. Krasovskaya, Yulia H. Budnikova

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Testing Lipophilic Cyclic(Alkyl)(Amino)Carbene-Based Ruthenium Benzylidene Catalysts in Cross Metathesis of 1-Dodecene at Ultralow Loadings (Below One Part-Per-Million) 超低负荷（低于百万分之一）下亲脂性环（烷基）（氨基）卡本基钌苄基催化剂1-十二烯交叉分解的测试

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-07 DOI: 10.1002/cctc.202500753

Adrian Sytniczuk, Karol Grela

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Single-Atom Zn Catalyst with ZnNx Active Sites Efficiently Promoted Meerwein–Ponndorf–Verley Reduction of Biomass-Derived Carbonyl Compounds 具有ZnNx活性位的单原子Zn催化剂有效促进生物质衍生羰基化合物的Meerwein-Ponndorf-Verley还原

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-06 DOI: 10.1002/cctc.202500961

Long Tao, Zhaoxi Cai, Chenglei Xiao, Yayun Pang, Jinpeng Liang, Prof. Jinliang Song

{"title":"Single-Atom Zn Catalyst with ZnNx Active Sites Efficiently Promoted Meerwein–Ponndorf–Verley Reduction of Biomass-Derived Carbonyl Compounds","authors":"Long Tao, Zhaoxi Cai, Chenglei Xiao, Yayun Pang, Jinpeng Liang, Prof. Jinliang Song","doi":"10.1002/cctc.202500961","DOIUrl":"https://doi.org/10.1002/cctc.202500961","url":null,"abstract":"Meerwein–Ponndorf–Verley (MPV) reduction is a highly promising strategy to selectively convert biomass-derived carbonyl compounds. Cost-effective and efficient heterogeneous catalysts for MPV reduction are still highly desired. In this study, N-doped carbon-supported Zn-based catalytic materials (denoted as Zn@C-T, in which T was the pyrolysis temperature) was fabricated by the pyrolysis of Zn-based coordination polymer formed from ZnCl2 and polyvinyl pyrrolidone. Very interestingly, the material prepared at 900 °C (Zn@C-900) showed excellent catalytic activity on MPV reduction of various biomass-derived carbonyl compounds to generate the corresponding alcohols, originating from the formed ZnNx sites in Zn@C-900. Especially, the usage of Zn was only 0.6 mol%, which was much lower than the usage of Zr in the popular Zr-based catalysts, confirming the great potential of the Zn@C-900 in large-scale applications. Systematic investigations revealed that the excellent catalytic activity of Zn@C-900 was predominantly enabled by the synergistic effect of Zn (as Lewis acid sites) and N (as Lewis base sites) in the ZnNx sites, which could simultaneously activate the carbonyl group in carbonyl compounds and the hydroxyl group in isopropanol, thereby significantly promoting the MPV reduction of carbonyl compounds. This work provided a cost-effective and efficient Zn-based catalyst for MPV reduction of biomass-derived carbonyl compounds.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237197","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

Efficient Electrosynthesis of Azo Derivatives Using Binder-Free Electrodeposited Organic/Ni-Co Nanohybrid Electrocatalyst 利用无粘结剂电沉积有机/镍钴纳米杂化电催化剂高效电合成偶氮衍生物

IF 3.9 3区化学

ChemCatChem Pub Date : 2025-08-06 DOI: 10.1002/cctc.202500608

Lalita Wagh, Devraj Singh, Arati Samal, Anushree Jain, Apurba K. Das

{"title":"Efficient Electrosynthesis of Azo Derivatives Using Binder-Free Electrodeposited Organic/Ni-Co Nanohybrid Electrocatalyst","authors":"Lalita Wagh, Devraj Singh, Arati Samal, Anushree Jain, Apurba K. Das","doi":"10.1002/cctc.202500608","DOIUrl":"https://doi.org/10.1002/cctc.202500608","url":null,"abstract":"In synthetic chemistry and pharmaceuticals, azo aromatics are important building blocks with a wide range of applications. However, their environmentally-friendly synthesis has not been extensively studied. Herein, we have synthesized the peptide bolaamphiphile-based organic–inorganic nanohybrid architecture, on a nickel foam (NF) substrate. The electrodeposition method is used to synthesize a Bola/Ni-Co nanohybrid (Bola = FW-AdiA-WF/Ni-Co, AdiA = adipic acid, W = L-tryptophan, F = L-phenylalanine, Ni = nickel nitrate and Co = cobalt nitrate (2:2)) on nickel foam without the need for any additional conductive material or binder. The resulting electrocatalyst is highly effective in selectively facilitating the anodic azo coupling reaction (ACR) of aromatic amines, converting them into azo aromatics at ambient conditions. This reaction takes place in a 1 M KOH electrolyte at a current density of 15 mA in an undivided cell. The electrocatalyst is effective for a broad range of substrates and can tolerate various functional groups. During the electrosynthesis of azo aromatics, the substrate adheres to the surface of electrocatalyst, which prevents the competing oxygen evolution reaction (OER). The use of water as a solvent avoids the need for excessive chemicals, making this electrosynthesis method safe, cost-effective, and environmentally friendly. Furthermore, the electrocatalyst is highly stable and can be reused for up to seven consecutive cycles. This method offers an energy-efficient route for the synthesis of value-added products with high yields for future prospectives.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237198","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