Catalysis Science & Technology最新文献

Characterizing Y224 conformational flexibility in FtmOx1-catalysis using ¹⁹F NMR spectroscopy.

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-20 DOI: 10.1039/d4cy01077a

Xinye Wang, Lingyun Yang, Shenlin Wang, Jun Wang, Kelin Li, Nathchar Naowarojna, Yi Ju, Ke Ye, Yuchen Han, Wupeng Yan, Xueting Liu, Lixin Zhang, Pinghua Liu

{"title":"Characterizing Y224 conformational flexibility in FtmOx1-catalysis using 19F NMR spectroscopy.","authors":"Xinye Wang, Lingyun Yang, Shenlin Wang, Jun Wang, Kelin Li, Nathchar Naowarojna, Yi Ju, Ke Ye, Yuchen Han, Wupeng Yan, Xueting Liu, Lixin Zhang, Pinghua Liu","doi":"10.1039/d4cy01077a","DOIUrl":"10.1039/d4cy01077a","url":null,"abstract":"α-Ketoglutarate-dependent non-haem iron (αKG-NHFe) enzymes play a crucial role in natural product biosynthesis, and in some cases exhibiting multifunctional catalysis capability. This study focuses on αKG-NHFe enzyme FtmOx1, which catalyzes endoperoxidation, dealkylation, and alcohol oxidation reactions in verruculogen biosynthesis. We explore the hypothesis that the conformational dynamics of the active site Y224 confer the multifunctional activities of FtmOx1-catalysis. Utilizing Y224-to-3,5-difluorotyrosine-substituted FtmOx1, produced via the amber codon suppression method, we conducted 19F NMR characterization to investigate FtmOx1's structural flexibility. Subsequent biochemical and X-ray crystallographic analyses provided insights into how specific conformations of FtmOx1-substrate complexes influence their catalytic activities. These findings underscore the utility of 19F NMR as a powerful tool for elucidating the complex mechanisms of multifunctional enzymes, offering potential avenues for developing biocatalytic processes to produce novel therapeutic agents harnessing their unique catalytic properties.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" ","pages":""},"PeriodicalIF":4.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11629144/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816799","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

Lanthanum-doped nickel-based composite metal oxide catalyst for hydrogenation of isophthalonitrile to produce meta-xylenediamine†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-13 DOI: 10.1039/D4CY00802B

Heng Shao, Jing Guo, Rulong Li, Dekun Ji, Long Huang and Haibin Chu

{"title":"Lanthanum-doped nickel-based composite metal oxide catalyst for hydrogenation of isophthalonitrile to produce meta-xylenediamine†","authors":"Heng Shao, Jing Guo, Rulong Li, Dekun Ji, Long Huang and Haibin Chu","doi":"10.1039/D4CY00802B","DOIUrl":"https://doi.org/10.1039/D4CY00802B","url":null,"abstract":"NiMAl (4 : 3 : 1)-LDO (M = Ca, Ba, and Mg) catalysts were prepared by co-precipitation. The optimal Ni4Mg3Al catalyst was selected and further modified with La to create the Ni4Mg3La0.15Al composite metal oxide catalyst. Under optimised reaction conditions, the isophthalonitrile (IPN) conversion reached 100%, and the selectivity to the target product meta-xylenediamine (MXDA) was remarkably high at 98.68%, while the selectivity of the by-product was as low as 0.05%. After ten reaction cycles, no significant decrease in the IPN conversion or MXDA selectivity was observed. The catalyst also exhibited excellent stability in a fixed-bed reactor over 400 hours, with the IPN conversion remaining at above 99% and MXDA selectivity maintained at an average of around 90%. The characterization results of the catalyst revealed that La addition strengthened the interaction between active Ni and the support, increased the content of strong basic sites in the catalyst, reduced the Ni nanoparticle size, and improved dispersion, leading to improved catalytic activity and stability.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7182-7190"},"PeriodicalIF":4.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798128","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

IBzH (IBenzhydryl): sterically-flexible N-aliphatic N-heterocyclic carbenes (NHCs) for iron-catalyzed C(sp3)–C(sp2) cross-coupling of unactivated haloalkanes† IBzH（IBenzhydryl）：立体灵活的 N-脂肪族 N-杂环碳烯 (NHC)，用于铁催化未活化卤代烃的 C(sp3)-C(sp2)交叉偶联†。

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-12 DOI: 10.1039/D4CY01315H

Marlena Kardela, Błażej Dziuk, Roman Szostak, Michal Szostak and Elwira Bisz

{"title":"IBzH (IBenzhydryl): sterically-flexible N-aliphatic N-heterocyclic carbenes (NHCs) for iron-catalyzed C(sp3)–C(sp2) cross-coupling of unactivated haloalkanes†","authors":"Marlena Kardela, Błażej Dziuk, Roman Szostak, Michal Szostak and Elwira Bisz","doi":"10.1039/D4CY01315H","DOIUrl":"https://doi.org/10.1039/D4CY01315H","url":null,"abstract":"Iron-catalyzed cross-coupling has emerged as a pivotal concept for the synthesis of valuable products across various facets of chemical research, including pharmaceuticals, organic materials and biological probes. In this respect, the use of N-heterocyclic carbenes (NHCs) as ancillary ligands to iron has been particularly effective. However, the major limitation is that the successful iron-catalytic systems have been almost exclusively limited to N-aryl-N-heterocyclic carbenes, which significantly restricts future developments of this commanding catalysis platform. Herein, we report IBzH (IBenzhydryl), a class of N-heterocyclic carbenes that are based on benzhydryl substitution of the imidazole ring. We demonstrate that this N-alkyl yet sterically-flexible ligand class promote the challenging C(sp3)–C(sp2) iron-catalyzed cross-coupling of unactivated haloalkanes, superseding the performance of other NHC ligands. Alkyl–alkyl cross-coupling is also described. Large scale synthesis and the evaluation of steric and electronic properties is presented. Considering the major advantages of sterically-flexible N-heterocyclic carbenes, we anticipate that this class of N-alkyl NHC ligands will have broad application.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7002-7008"},"PeriodicalIF":4.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798102","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

Anthracene-based covalent organic framework supported palladium nanoparticles for visible-light-mediated Suzuki–Miyaura cross-coupling†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-12 DOI: 10.1039/D4CY01083C

Lei Li, Qiujie Shan, Jiyuan Zang, Lei Yu, David J. Young, Zhi-Gang Ren and Hong-Xi Li

引用次数: 0

Bifunctional catalysts based on PdZn/ZnO and hierarchical zeolites in the direct synthesis of dimethyl ether from CO-rich syngas: influence of the support and the Zn/Pd molar ratio†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-11 DOI: 10.1039/D4CY00860J

Bing Wang, Nicola Da Roit, Michael Zimmermann, Markus Boese, Thomas Zevaco and Silke Behrens

{"title":"Bifunctional catalysts based on PdZn/ZnO and hierarchical zeolites in the direct synthesis of dimethyl ether from CO-rich syngas: influence of the support and the Zn/Pd molar ratio†","authors":"Bing Wang, Nicola Da Roit, Michael Zimmermann, Markus Boese, Thomas Zevaco and Silke Behrens","doi":"10.1039/D4CY00860J","DOIUrl":"https://doi.org/10.1039/D4CY00860J","url":null,"abstract":"Following the ‘precursor’ concept, a series of Pd/Zn-based, colloidal nanoparticles (NPs) with different Zn/Pd molar ratios were synthesized by reductive stabilization and used as precursors for the methanol active component in bifunctional catalysts. The bifunctional catalysts for the single-step dimethyl ether synthesis from CO-rich syngas were obtained by immobilizing the NPs on a microporous or hierarchical HZSM-5 zeolite, which were used as dehydration catalysts. The catalysts were characterized, e.g., by (in situ) powder X-ray diffraction, scanning and transmission electron microscopy with energy-dispersive X-ray analysis, N2 physisorption, and NH3 temperature programmed desorption. This study demonstrates the influence of the Zn/Pd molar ratio on the size of PdZn particles formed under reaction conditions, which correlates with the catalytic performance in the STD process. The introduction of mesopores in the hierarchical zeolite by desilication of HZSM-5 increased the DME yield while decreasing the selectivity to hydrocarbons.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7152-7162"},"PeriodicalIF":4.4,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00860j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798125","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

The O2-stable [FeFe]-hydrogenase CbA5H reveals high resilience against organic solvents†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-07 DOI: 10.1039/D4CY01018C

Martin Gerbaulet, Anja Hemschemeier and Thomas Happe

{"title":"The O2-stable [FeFe]-hydrogenase CbA5H reveals high resilience against organic solvents†","authors":"Martin Gerbaulet, Anja Hemschemeier and Thomas Happe","doi":"10.1039/D4CY01018C","DOIUrl":"https://doi.org/10.1039/D4CY01018C","url":null,"abstract":"[FeFe]-Hydrogenases are highly efficient hydrogen-(H2) converting enzymes which play pivotal roles for H2 cycling in natural habitats, but which are also of interest for sustainable approaches to generate or employ H2 gas. [FeFe]-Hydrogenases harbor a unique active site metal cofactor, the H-cluster, whose di-iron site by itself is nearly inactive but, as part of the protein, allows high turnover rates. Understanding this essential interplay of protein and co-factor might help to install [FeFe]-hydrogenases in biotechnological applications. The catalytic unit of the H-Cluster can be synthesized chemically and incorporated into [FeFe]-hydrogenase precursors, which allows to introduce non-natural metals or ligands and study their impact on catalytic activity. However, these compounds are often not water-soluble and have to be added to the proteins in solvents known to destabilize polypeptides. The resilience of [FeFe]-hydrogenases against organic solvents has hardly been investigated. To address this knowledge gap, we characterized the stability of the [FeFe]-hydrogenase CbA5H from Clostridium beijerinckii in several organic solvents (dimethylsulfoxide (DMSO), acetone, acetonitrile as well as water-miscible short-chain alcohols). These solvents are required to dissolve co-factor analogues and are also employed in chemical syntheses that might be combined with biocatalysts such as hydrogenases for more sustainable industrial processes. In the medium time-frame, CbA5H is remarkably stable in high concentrations of acetone and acetonitrile and also withstands intermediate concentrations of DMSO, ethanol and methanol. Combined with the unusual O2 stability and high temperature and pressure tolerance, this makes CbA5H a candidate for its use in non-aqueous reaction environments.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7093-7106"},"PeriodicalIF":4.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01018c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798120","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

Insight into the influence of Re and Cl on Ag catalysts in ethylene epoxidation. 深入了解 Re 和 Cl 对乙烯环氧化中银催化剂的影响。

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-06 DOI: 10.1039/d4cy00858h

Claudia J Keijzer, Pim T Weide, Kristiaan H Helfferich, Justyna Zieciak, Marco de Ridder, Remco Dalebout, Tracy L Lohr, John R Lockemeyer, Peter van den Brink, Petra E de Jongh

{"title":"Insight into the influence of Re and Cl on Ag catalysts in ethylene epoxidation.","authors":"Claudia J Keijzer, Pim T Weide, Kristiaan H Helfferich, Justyna Zieciak, Marco de Ridder, Remco Dalebout, Tracy L Lohr, John R Lockemeyer, Peter van den Brink, Petra E de Jongh","doi":"10.1039/d4cy00858h","DOIUrl":"10.1039/d4cy00858h","url":null,"abstract":"Commercial ethylene epoxidation catalysts consist of α-alumina supported Ag particles and usually contain a mixture of promoters. High selectivity catalysts typically include a small amount of rhenium species. We studied a series of Ag catalysts promoted with Re loadings up to 4 at% (Re/(Re + Ag)), which is intentionally higher than in optimized commercial catalysts to facilitate characterization and to amplify the influence on catalysis. Sequential impregnation brought Re and Ag in such close contact that they formed a new characterized phase of AgReO4. Chemisorption experiments showed that both ReO x and AgReO4 species act as a reversible reservoir for O2. Ethylene epoxidation was performed without and with the industrially crucial ethyl chloride promoter in the feed. Without the chloride (Cl), the ethylene oxide selectivity increased when Re was present, whereas the combination of Re and Cl decreased the ethylene oxide selectivity at higher Re loadings. Systematic ethylene oxide isomerization experiments revealed that Re and Cl individually inhibit the isomerization on the Ag surface. However, Re and Cl combined increased the isomerization, which can be explained by the surface becoming overly electrophilic. This hence shows the importance of studying promoters both individually and combined.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" ","pages":""},"PeriodicalIF":4.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11563198/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646022","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

Deciphering the role of chemisorbed CO in CO2 methanation: kinetic and mechanistic investigation over monometallic (Ru) and bimetallic (Ru–Ni) catalysts† 解读化学吸附 CO 在 CO2 甲烷化过程中的作用：单金属（Ru）和双金属（Ru-Ni）催化剂的动力学和机理研究†。

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-05 DOI: 10.1039/D4CY01004C

Pavan Dongapure, Jyoti Tekawadia, V. Satyam Naidu and R. Nandini Devi

{"title":"Deciphering the role of chemisorbed CO in CO2 methanation: kinetic and mechanistic investigation over monometallic (Ru) and bimetallic (Ru–Ni) catalysts†","authors":"Pavan Dongapure, Jyoti Tekawadia, V. Satyam Naidu and R. Nandini Devi","doi":"10.1039/D4CY01004C","DOIUrl":"https://doi.org/10.1039/D4CY01004C","url":null,"abstract":"Supported metal catalysts have made prominent contributions to CO2 mitigation through conversion into useful chemicals. However, intermediates and mechanisms involved in this process remain ambiguous. Herein, we present the kinetics, mechanistic route and impact of chemisorbed CO in CO2 methanation on Ru/γ-Al2O3 and Ru–Ni/γ-Al2O3 catalysts. Both the catalysts show minimal variation in adsorbed species on changing the duration of reduction, as confirmed through in situ IR spectroscopy. A notable observation is that the adsorbed CO exhibits a red shift at a longer reduction time and a more reactive nature on the Ru/γ-Al2O3 surface. Conversely, stable bridged CO mode is detected on Ru–Ni/γ-Al2O3 under similar conditions, leading to catalyst poisoning in all instances. This indicates that pre-reduction duration does not have much effect on the surface but interference of CO has more effect at lower concentrations of reactant gases. In situ XRD analysis reveals limited changes in the metallic or mixed oxide species during these conditions. Reaction kinetic analysis showed that Ru–Ni/γ-Al2O3 has better rate performance at higher concentrations of CO2, whereas Ru/γ-Al2O3 exhibits better rate performance at lower concentrations. The activation energy was found to be 74.07 kJ per mole for Ru/γ-Al2O3 and 89.38 kJ per mole for Ru–Ni/γ-Al2O3. The turnover frequency (TOF) is directly proportional to the rate of formation of methane.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7124-7133"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798122","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

Effects of zeolite porosity and acidity on catalytic conversion of carbohydrates to bio-based chemicals: a review

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-05 DOI: 10.1039/D4CY01070A

Deyu Chu, Jinjing Ma, Qishun Liu, Jie Fu and Heng Yin

引用次数: 0

Mechanistic study of DETA-modified CdS for carbon dioxide reduction† DETA 改性 CdS 用于二氧化碳还原的机理研究†。

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2024-11-01 DOI: 10.1039/D4CY01140F

Meiyan Guo, Wanxiang Yang, Yi Li, Yongfan Zhang and Wei Lin

{"title":"Mechanistic study of DETA-modified CdS for carbon dioxide reduction†","authors":"Meiyan Guo, Wanxiang Yang, Yi Li, Yongfan Zhang and Wei Lin","doi":"10.1039/D4CY01140F","DOIUrl":"https://doi.org/10.1039/D4CY01140F","url":null,"abstract":"Cadmium sulfide (CdS) exhibits remarkable light absorption capabilities and is widely employed in photocatalytic reduction of CO2. Nevertheless, the crystal facet effects on the micro-scale mechanisms governing CO2 conversion on CdS remain elusive. This study theoretically investigates the electronic properties of hexagonal-phase (101), (001), and cubic-phase (111) CdS surfaces modified with diethylenetriamine (DETA). From a microscopic viewpoint, it elucidates the unique bonding characteristics of CO2 on different exposed facets of DETA/CdS and the formation mechanisms leading to products such as CO, HCOOH, CH2O, CH3OH, and CH4. Our findings reveal that the DETA/CdS(101) surface is the most stable, effectively adsorbing hydrogen and CO2 at varied Cd sites with a high selectivity towards CO production, thereby showing promise for syngas generation, albeit with potential yields of formic acid and methane. Conversely, DETA/CdS(001) and (111) primarily facilitate the reduction of CO2 to CH4. These discoveries offer theoretical insights into photochemical experiments involving CO2 reduction on CdS, shedding light on the influence of crystal facets on reaction pathways.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7172-7181"},"PeriodicalIF":4.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798127","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