ChemCatChem最新文献

{"title":"Chemoenzymatic Cascade Synthesis of Metal-Chelating α-Amino Acids","authors":"Sophie H. Young,&nbsp;James S. Andon,&nbsp;Jooyeon Lim,&nbsp;Mareena C. Franke,&nbsp;Prof. Daniel J. Weix,&nbsp;Prof. Tina Wang,&nbsp;Prof. Andrew R. Buller","doi":"10.1002/cctc.202401958","DOIUrl":"https://doi.org/10.1002/cctc.202401958","url":null,"abstract":"<p>Metal-chelating noncanonical amino acids (ncAAs) are uniquely functional building blocks for proteins, peptide catalysts, and small molecule sensors. However, catalytic asymmetric approaches to synthesizing these molecules are hindered by their functional group variability and intrinsic propensity to ligate metals. In particular, bipyridyl-<span>l</span>-alanine (BpyAla) is a highly sought ncAA, but its complex, inefficient syntheses have limited utility. Here, we develop a chemoenzymatic approach to efficiently construct BpyAla. Three enzymes that can be produced in high titer together react to convert Gly and an aldehyde into the corresponding β-hydroxy ncAA, which is subsequently deoxygenated. We explore approaches to synthesizing biaryl aldehydes and show how the three-enzymatic cascade can access a range of α-amino acids with bulky side chains, including a variety of metal-chelating amino acids. We show that newly accessible BpyAla analogues are compatible with existing amber suppression technology, which will enable future merging of traditional synthetic and biosynthetic approaches to tuning metal reactivity.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202401958","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565355","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}

{"title":"Hydrogen Release From Ammonia: Size and Support Effects in Heterogeneous Transition Metal Catalysis","authors":"Jihao Wang,&nbsp;Shilong Chen,&nbsp;Malte Behrens","doi":"10.1002/cctc.202400860","DOIUrl":"https://doi.org/10.1002/cctc.202400860","url":null,"abstract":"<p>Ammonia, industrially produced by the Haber–Bosch process, can serve as a promising renewable energy carrier based on its high hydrogen content and energy density as well as its full-fledged infrastructure worldwide for transportation. Renewable hydrogen will be converted firstly in ammonia synthesis, stored and/or transported bound in ammonia, and released on demand by ammonia decomposition. So far, the most active catalysts for the decomposition reaction are Ru-based due to its optimal nitrogen binding energy compared to other transition metals. However, due to the high cost of Ru, the development of alternative catalysts for ammonia decomposition is attractive, especially non-noble transition metals such as Fe, Ni, or Co. For supported metal catalysts, size and support effects play important roles in the catalytic reaction, resulting in a change of their geometric and/or electronic properties. In this review, we first discuss and comment on representative existing studies of the size and support effects of Ru, Fe, Ni, and Co catalysts in ammonia decomposition from an experimental and theoretical view, suggesting possible reasons for geometrical and electronic effects. Afterward, we will summarize the available catalytic data in the literature in the form of TOF_H2 and reaction rate of each supported transition-metal catalyst with different supports as a function of the particle size, attempting to identify an optimum particle size and a trend for the different supports. Finally, we will discuss the challenges and perspectives of future-oriented research on the size and support effect in ammonia decomposition.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202400860","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565333","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}

{"title":"Anaerobic Catalyst Design for Alcohol Oxidation: Fine-Tuning Copper/TEMPO with Bipyridine Proportions","authors":"Matheus G. B. Rodrigues,&nbsp;André L. Pesquero de Melo,&nbsp;Maurício D. Coutinho-Neto,&nbsp;Camilo A. Angelucci","doi":"10.1002/cctc.202401444","DOIUrl":"https://doi.org/10.1002/cctc.202401444","url":null,"abstract":"<p>In this study, we investigate the indirect electro-oxidation of benzyl alcohol (BA) using the copper/TEMPO catalytic system, which combines copper complexes with 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) in an anaerobic medium. We reexamine the impact of bpy ligand proportions, exploring ratios of 1:1, 2:1, 3:1, and 4:1 on catalytic activity. Cyclic voltammetry and visible spectroscopy reveal distinct electrochemical characteristics and complex formations at different bpy ratios. Simulations uncover intricate energy equilibria involving ion coordination, varying with oxidation state, and bpy proportion. Theoretical and experimental spectra align, supporting the proposed structures. The Brønsted base, triethylamine (TEA), essential in this anaerobic system, shows different voltammetric profiles with each ligand ratio, revealing key interactions with bpy complexes. In the presence of BA, the 1:1 and 2:1 ratios exhibit indirect catalytic activity, with the 2:1 ratio yielding significantly higher current densities. This establishes a new optimal condition where <span></span><math></math> formed in a 2:1 stoichiometry demonstrates superior activity with a lower redox potential, while maintaining labile coordination points for necessary interactions. Theoretical results also indicate weaker TEMPO coordination to <span></span><math></math>.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565329","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}

{"title":"Gold Nanoparticle-Catalyzed Solvent Switchable Selective Partial Reduction of Nitrobenzene to N-Phenylhydroxylamine and Azoxybenzene","authors":"Dr. Simon Doherty,&nbsp;Dr. Julian G. Knight,&nbsp;Dr. Hussam Y. Alharbi,&nbsp;Reece Paterson,&nbsp;Dr. Corinne Wills,&nbsp;Dr. Casey Dixon,&nbsp;Prof. Thomas W. Chamberlain,&nbsp;Han Yan,&nbsp;Dr. Anthony Griffiths,&nbsp;Dr. Helen Daly,&nbsp;Dr. Sarayute Chansai,&nbsp;Prof. Christopher Hardacre","doi":"10.1002/cctc.202401702","DOIUrl":"https://doi.org/10.1002/cctc.202401702","url":null,"abstract":"<p>Impregnation of phosphine-decorated polymer-immobilized ionic liquid with the tetrachloroaurate anion results in reduction of the gold(III) to gold(I) with concomitant oxidation of the phosphine to its oxide. In situ reduction of the resulting precursor, AuCl@O = PPh₂-PEGPIILS, generated the corresponding O = PPh₂-PEGPIIL-stabilized AuNPs, AuNP@O = PPh₂-PEGPIILS, which is a highly active and selective catalyst for the solvent-dependent partial reduction of nitrobenzene to <i>N</i>-phenylhydroxylamine in water and azoxybenzene in ethanol. The initial TOFs are comparable to those obtained with gold nanoparticles generated by reduction of tetrachloroaurate-impregnated phosphine oxide-decorated polymer-immobilized ionic liquid AuCl₄@O = PPh₂-PEGPIILS, i.e., the activity and selectivity profiles do not appear to depend on whether the AuNPs are generated from Au(III) or in situ-generated Au(I). In stark contrast, gold nanoparticles prepared by NaBH₄ reduction of AuCl@PPh₂-PEGPIILS based on gold(I) confined in phosphine-modified polymer-immobilized ionic liquid gave markedly lower initial TOFs. The use of dimethylamine borane (DMAB) as the hydrogen donor resulted in a substantial and dramatic enhancement in activity for reductions conducted in water compared with NaBH₄ and the initial TOF of 20,400 mol nitrobenzene converted mol Au⁻¹ h⁻¹ obtained with AuNPs generated in situ from AuCl₄@O = PPh₂-PEGPIILS is among the highest to be reported for the metal nanoparticle catalyzed selective reduction of nitrobenzene to <i>N</i>-phenylhydroxylamine; this is a significant improvement on existing protocols, which should enable the partial selective reduction of nitroarenes to be conducted in water with a low catalyst loading under extremely mild conditions.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202401702","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565331","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}

{"title":"Front Cover: Au Clusters Catalyze The Disulfide Metathesis Reaction By A Reductive Addition-Oxidative Elimination Mechanism (ChemCatChem 23/2024)","authors":"Belén Lerma-Berlanga,&nbsp;Francesco Orlando,&nbsp;Estíbaliz Merino,&nbsp;Antonio Leyva-Pérez","doi":"10.1002/cctc.202482301","DOIUrl":"https://doi.org/10.1002/cctc.202482301","url":null,"abstract":"<p>\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"16 23","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202482301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142860529","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}

{"title":"Propane Dehydrogenation Over Silicalite-1 Supported PtMn Catalyst with Low Pt Loading","authors":"Wenxin Wang,&nbsp;Huimin Hu,&nbsp;Jiaxin Song,&nbsp;Xiaoqiang Fan,&nbsp;Xuehua Yu,&nbsp;Lian Kong,&nbsp;Xia Xiao,&nbsp;Zean Xie,&nbsp;Zhen Zhao","doi":"10.1002/cctc.202401799","DOIUrl":"https://doi.org/10.1002/cctc.202401799","url":null,"abstract":"<p>Pt-based catalysts have been widely studied for propane dehydrogenation (PDH) because of their high activity and environmental sustainability. However, as a precious metal, the development of catalysts with high stability and low Pt content is of great significance. In this study, a series of silicalite-1 (S-1) supported PtMn (0.1PtxMn/S-1) catalysts with low Pt loading amount (0.1 wt%) was prepared. The effects of different Mn loadings on the physicochemical properties and catalytic performance in the PDH reaction were studied. The addition of an appropriate amount of Mn regulated the dispersion of Pt particles and increased the number of active sites of the catalyst, enhancing the catalytic performance of PDH even at a low Pt loading. The initial propane conversion was 46.1% over 0.1Pt0.3Mn/S-1 catalyst, and the deactivation rate constant was the lowest of 0.01 h⁻¹. This may be because of an appropriate Mn loading was beneficial for enhancing the interaction between the metal and the support, forming MnO_<i>x</i> is attached to the S-1 surface, while the surface of MnO_<i>x</i> stabilized the PtMn alloy, thereby improving the catalytic performance for PDH.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565330","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}

{"title":"Cu/ZnO/Al2O3 Catalyst Promoted with Amorphous MgO for Enhanced CO2 Hydrogenation to Methanol","authors":"Hecao Chen,&nbsp;Shangzhi Xie,&nbsp;Zhaocong Jiang,&nbsp;Jing Xu,&nbsp;Minghui Zhu","doi":"10.1002/cctc.202401687","DOIUrl":"https://doi.org/10.1002/cctc.202401687","url":null,"abstract":"<p>CO₂ hydrogenation to methanol not only reduces CO₂ emissions but also produces a high-quality energy source that is easy to store and transport. We found that the Cu/ZnO/Al₂O₃/MgO catalyst prepared by the deposition-precipitation method, exhibits a higher methanol space-time yield compared to the Cu/ZnO/Al₂O₃ catalyst below 2 MPa. However, no activity difference was observed beyond 2 MPa. Characterization techniques revealed that for the Cu/ZnO/Al₂O₃/MgO catalyst, MgO is amorphous attributed to the influence of Al during calcination. The presence of amorphous MgO not only reduces the size of Cu⁰ particles but also enhances CO₂ adsorption on the catalyst surface. We also demonstrate that improvement of CO₂ adsorption capacity is the key factor for the higher activity of the Cu/ZnO/Al₂O₃/MgO catalyst below 2 MPa.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565093","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}

{"title":"Waste-Derived Catalyst for Biodiesel Manufacturing in CO2-Free Manner: Preparation, Catalytic Activity, and Reuse Studies","authors":"Anton N. Potorochenko,&nbsp;Yulia V. Gyrdymova,&nbsp;Konstantin S. Rodygin","doi":"10.1002/cctc.202401607","DOIUrl":"https://doi.org/10.1002/cctc.202401607","url":null,"abstract":"<p>Currently, CaO-based catalysts for biodiesel manufacturing are produced by calcination of available limestone ore consisting of CaCO₃. The production of 1 ton of CaO catalyst resulted in 0.89 tons of CO₂ emission, and every ton of the catalyst provided only 20 tons of biodiesel in nonreusable manner. In this study, a CaO-based catalyst was obtained by calcination of Ca(OH)₂, a large-tonnage waste from acetylene manufacturing via calcium carbide route (carbide slag), producing H₂O as a by-product instead of CO₂. Amazingly, carbide slag-a waste material-was active in catalytic transesterification of soybean oil skipping calcination or any pretreatment steps and provided biodiesel in 28% yield. Moreover, biodiesel was obtained in 98% yield after catalyst calcination at 600 °C for at least 4 times accompanying zero CO₂ emission. The obtained catalysts were characterized by XRD, XRF, FTIR, TGA, SEM-EDX, and BET surface area analysis. The best conversion of soybean oil was achieved using 1 wt% CS₆₀₀, MeOH:oil ratio of 12:1, by boiling at 65 °C for 2 h. The catalyst reuse was found out using two approaches: “catalyst isolation” (5 cycles with yield ≥ 80%) and “fresh start” (up to 7–10 cycles with yield ≥ 80%).</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143564975","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}

{"title":"Electrocatalytic Stability Over Ruthenium-Based Catalysts for Proton Exchange Membrane Water Electrolysis","authors":"Yu Zhang,&nbsp;Wenwen Huang,&nbsp;Hehe Wei","doi":"10.1002/cctc.202401707","DOIUrl":"https://doi.org/10.1002/cctc.202401707","url":null,"abstract":"<p>Achieving large-scale, low-cost hydrogen production through proton exchange membrane water electrolysis (PEMWE) is a key strategic direction in the energy revolution. However, the high potential of oxygen evolution reaction (OER) and the acidic environment seriously limit the hydrogen production efficiency. RuO₂-based catalysts have garnered significant attention due to their unique electronic structure and exceptional activity in the OER. Nevertheless, their durability remains insufficient for long-term PEMWE and hydrogen generation. This paper explores the fundamental causes of catalyst degradation and strategies to enhance the catalyst stability under different reaction pathways. Additionally, the importance of PEMWE components, including bipolar plates and membrane electrode assemblies, in improving system stability and efficiency is emphasized, highlighting their role in large-scale applications of PEMWE. Looking forward, research efforts should prioritize the optimization of both catalysts and system components to achieve a balance between the performance, cost, and long-term durability. By addressing these factors, we can unlock the full potential of PEMWE technology and make hydrogen a viable, large-scale solution for clean energy production.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143564977","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}

{"title":"Mechanistic Investigations on the Direct Regioselective Sulfonation of Gaseous Light Hydrocarbons by Sulfur Dioxide","authors":"Jen-Chieh Wang,&nbsp;Sungah Kim,&nbsp;Joo Ho Lee,&nbsp;Carlos Ascencio,&nbsp;Lynn Chung,&nbsp;Julia Cashman,&nbsp;Kyung Woon Jung","doi":"10.1002/cctc.202401970","DOIUrl":"https://doi.org/10.1002/cctc.202401970","url":null,"abstract":"<p>Gaseous light hydrocarbons (LHs) are traditionally used as fuels, while their functionalization leads to wide applications of high economical values. Presented herein is the direct sulfonation of gaseous LHs by using SO₂ and O₂ gases. The in situ-generated trifluoroperacetic acid (TFAOOH) and bis(trifluoroacetyl) peroxide ((TFAO)₂) furnished the radical propagators trifluoroacetoxyl radicals (TFAO•) and HO•. The resultant trifluoroacetylsulfuric acid (TFAOSO₃H) efficiently sulfonated LHs under mild conditions and in good chemoselectivities.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 5","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143564976","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}