Molecular Catalysis最新文献

{"title":"Theoretical insight on the delicate regulation of coordination environments for carbon-nitrogen-supported single-atom metals for OER and ORR","authors":"Xiao-Kuan Wu,&nbsp;Junan Gao,&nbsp;Zhao Hong,&nbsp;Zhigang Lei,&nbsp;Jie Zhang","doi":"10.1016/j.mcat.2024.114784","DOIUrl":"10.1016/j.mcat.2024.114784","url":null,"abstract":"<div><div>Carbon-nitrogen-supported single-atom catalysts have significant potential in electrochemistry; however, the real active site TM-C<em>_x</em>-N<em>_y</em> structures are typically complex and varied due to the high-temperature preparation conditions. In order to systematically identify the activity and intrinsic mechanism of these reaction sites, the density-functional theory was employed, whereby different TM-C<em>_x</em>-N<em>_y</em> structures were constructed by quantitative N-atom doping using graphene as a substrate. The adsorption strength of the intermediates and the catalyst activity were effectively regulated by precisely controlling the coordination of the single-atom metals. The findings indicate that the majority of TM-C<em>_x</em>-N<em>_y</em> exhibit robust thermodynamic and electrochemical stability. Among these, Ni-C₄, Co-N₄, and Rh-N₄ demonstrate the most promising OER and ORR activities. By calculating the modulation interval of intermediate adsorption energies from TM-C₄ to TM-N₄, it was found that metals with different valence electrons exhibit disparate sensitivities to coordination modulation with Group VIII(II) elements (N<em>_e</em> = 9) showing the highest modulation efficiency, which is further substantiated by charge density difference and Bader charge analyses employing Co and Au as illustrative examples. Furthermore, a desirable descriptor, termed φ, has been identified, which correlates well with the intermediate adsorption energy and η^OER/ORR, thus allowing an accurate representation of the activity of various TM-C<em>_x</em>-N<em>_y</em> structures. The catalyst exhibits optimum activity when the φ value is within the range of 120–130. However, when the value of φ exceeds 150, it is no longer reliable for evaluating the activity of the catalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114784"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146961","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Competitive effects of polymeric ligands molecular weight on the gold colloidal nanocatalysts: Impact of catalysts design and catalytic performance","authors":"Stefano Scurti ,&nbsp;Elena Rodríguez-Aguado ,&nbsp;Juan Antonio Cecilia ,&nbsp;Daniele Caretti ,&nbsp;Nikolaos Dimitratos","doi":"10.1016/j.mcat.2024.114780","DOIUrl":"10.1016/j.mcat.2024.114780","url":null,"abstract":"<div><div>This research investigates the influence of hydro-soluble polymeric ligands on the properties and catalytic performance of colloidal gold nanoparticles supported on activated carbon. The aim was to understand how polymer molecular weight affects Au nanoparticle size, dispersion, and catalytic activity, providing a framework for optimizing catalysis from the design phase. Three polymeric ligands (PVA, PEO, and PVAm) with different molecular weights were synthesized via controlled chain-transfer-to-solvent reactions and used to prepare supported colloidal Au nanoparticles through sol-immobilization. The results demonstrated that molecular weight significantly impacts Au nanoparticle size. Moreover, catalytic activity was assessed using the reduction of 4-nitrophenol as a model reaction. As polymer molecular weight increased, the apparent kinetic constant (k_app) decreased, particularly for PEO-based catalysts, where k_app decreased by an order of magnitude. Higher molecular weight polymers also formed dense polymeric \"brushes,\" hindering reagent diffusion and reducing catalytic performance. Further analysis of Au/polymer weight ratios revealed that decreasing polymer content improved catalytic activity, particularly in Au-PVAm catalysts. The findings underscore the crucial role of polymeric ligands in colloidal nanocatalyst design, emphasizing the need to investigate the metal-polymer interface to optimize catalyst properties.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114780"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rational regulation of efficient nitrogen-bridge heteronuclear metal electrocatalyst for nitrogen fixation","authors":"Shuo Wang,&nbsp;Likai Yan,&nbsp;Zhongmin Su","doi":"10.1016/j.mcat.2024.114794","DOIUrl":"10.1016/j.mcat.2024.114794","url":null,"abstract":"<div><div>As an extension of single-atom catalysts (SACs), bimetallic atom catalysts (BACs) have the advantages of higher metal loading, more flexible active sites, and potentially better catalytic performance. However, how to adjust the synergistic effect of two adjacent metal centers to improve the catalytic performance is imperative and challenging. In this work, different transition-metal (TM) atoms (V, Mn, Fe, Co, and Mo) were paired to form 10 kinds of N-bridge heteronuclear bimetals embedded into N-doped graphene, and the electrocatalytic performance of M1M2@NGs for N₂ reduction were predicted by using density functional theory (DFT) computations. By investigating the stability, activity, and selectivity, VMn@NG, VFe@NG, and VCo@NG are screened out as efficient catalysts for activating nitrogen and suppressing the competing hydrogen evolution reaction with low limiting potentials −0.35, −0.29, and −0.31 V for nitrogen reduction reaction (NRR), respectively. The electronic redistribution induced by the adjacent TM-N₄ moieties regulates the interaction between *N₂ intermediates and metal center thus accelerating NRR. The distribution of metal d orbitals can also be used to determine the dominant configuration of N₂ adsorption. Highly efficient and selective BACs for NRR can be screened based on the scaling relationship between the key intermediates (*N₂H and *NH₂). This work not only explores promising electrocatalysts for dinitrogen reduction but also paves a potential route for rationally designing heteronuclear double-site catalysts for other reactions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114794"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"ZrO2 stablishing CoO facilitates hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran","authors":"Kaiyun Lu ,&nbsp;Mingxiu Cao ,&nbsp;Yuxin Du ,&nbsp;Hao Huang ,&nbsp;Wenjie Xiang ,&nbsp;Guangbo Liu ,&nbsp;Jifan Li ,&nbsp;Chun-Ling Liu ,&nbsp;Noritatsu Tsubaki ,&nbsp;Wen-Sheng Dong","doi":"10.1016/j.mcat.2024.114765","DOIUrl":"10.1016/j.mcat.2024.114765","url":null,"abstract":"<div><div>The synthesis of high value-added 2,5-dimethylfuran (2,5-DMF) from catalytic hydrogenolysis of 5-hydroxymethylfurfural (5-HMF) is one of significant reactions for biomass utilization, but it still confronts big challenges for the development of base metal catalysts with high performance. In this work, we fabricated series of ZrO₂ modified Co nanocatalysts derived from layered double hydroxides (LDHs), wherein metastable state CoO species can be stablished via sacrifice of a portion of surface vacancies, for selective synthesis of 2,5-DMF via 5-HMF hydrogenolysis. The optimal catalyst 2ZrO₂-Co/Al₂O₃ shows great catalytic performance and good stability, which gives a high 2,5-DMF yield of up to 97.3 %. The addition of ZrO₂ stablishes the metastable state CoO species, which cooperate with suitable oxygen vacancies and enhance the adsorption of 5-HMF and heterolytic dissociation of H₂ to generate highly active H^δ− species, consequently achieving excellent catalytic performance for hydrogenolysis of 5-HMF to 2,5-DMF.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114765"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146890","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Alkane hydroxylation by m-CPBA catalyzed by Co(II)-complexes","authors":"Takumi Nakamura,&nbsp;Rin Ito,&nbsp;Hideki Sugimoto,&nbsp;Shinobu Itoh","doi":"10.1016/j.mcat.2024.114782","DOIUrl":"10.1016/j.mcat.2024.114782","url":null,"abstract":"<div><div>Catalytic activities of the cobalt(II) complexes supported by tripodal N₄-tetradentate ligands have been examined in the alkane hydroxylation reaction by <em>m</em>-CPBA (<em>m</em>-chloroperbenzoic acid). Detailed product analysis data have indicated that hydrogen atom abstraction (HAA) from the alkane substrates is a key step in the hydroxylation reaction, where not only the aroyloxy radical intermediate (ArC(O)O•; Ar = <em>m</em>-chlorophenyl)) derived from <em>m</em>-CPBA via O–O bond homolysis but also a Co–O• type intermediate is involved as a reactive oxidant. Significant effects of the supporting ligands and the metal ions (Fe^II, Ni^II, and Cu^II) support this mechanism.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114782"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of the Au-Ag morphology in the electrocatalytic reduction of organic halides","authors":"Ilaria Barlocco ,&nbsp;Stefano Cattaneo ,&nbsp;Silvio Bellomi ,&nbsp;Marta Stucchi ,&nbsp;Valentina Pifferi ,&nbsp;Juan J. Delgado ,&nbsp;Xiaowei Chen ,&nbsp;Luigi Falciola ,&nbsp;Laura Prati ,&nbsp;Alberto Villa","doi":"10.1016/j.mcat.2024.114762","DOIUrl":"10.1016/j.mcat.2024.114762","url":null,"abstract":"<div><div>Bimetallic gold-silver nanoparticles (NPs) have unique chemical and physical properties due to the synergistic effect of the two metals. From a catalytic point of view, supported AuAg NPs possess different properties depending on their structure, e.g. random alloy or core-shell. Herein, we synthesised bimetallic Au-Ag nanoparticles using a sol-immobilisation method to obtain different bimetallic structures. These colloids were then deposited on high heat-treated (HHT) carbon nanofibers characterised through high-resolution transmission microscopy coupled with energy-dispersive X-ray spectroscopy (HRTEM-EDX), and cyclic voltammetry (CV). Combining these complementary techniques revealed the formation of a random alloy, AuAg, and two core-shell structures, Ag@Au and Au@Ag. In the first case, the structure presents a silver shell and a gold core, while the second possesses a silver core covered in gold. Finally, the catalysts were tested in the electrocatalytic reduction of organic halides, i.e. acetobromo-α-D-glucose and benzyl bromide, two model well-studied molecules, and compared with the catalytic performance of the respective monometallic counterparts. For both the substrates the bimetallic NPs showed an increased reactivity compared to the monometallic counterparts, underlining the synergistic effect of the two metals. More importantly, the different structures assumed by the NPs had an impact on the catalytic activity. Indeed, the Ag@Au/HHT catalyst showed the lowest reduction potential for the reduction of acetobromo-α-D-glucose, while for benzyl bromide reduction the random alloy results to be the best employed catalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114762"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coating-modified foam ceramic catalysts for ethyl nicotinate hydrogenation","authors":"Fuxin Liang ,&nbsp;Yulin Wei ,&nbsp;Yuhang Du ,&nbsp;Fan Yang ,&nbsp;Zhe Pang ,&nbsp;Haochen Dang ,&nbsp;Junyan Wu ,&nbsp;Sai Huang ,&nbsp;Honglei Wang ,&nbsp;Qinggang Li ,&nbsp;Chao Wu ,&nbsp;Zhi Wang ,&nbsp;Guopu Shi","doi":"10.1016/j.mcat.2024.114785","DOIUrl":"10.1016/j.mcat.2024.114785","url":null,"abstract":"<div><div>In drug synthesis, ethyl nicotinate hydrogenation is commonly performed to prepare ethyl 3-piperidine-carboxylate. For this hydrogenation, it is crucial to explore a catalyst with high catalytic activity and selectivity to form the desired product. To this end, a series of Pd/Al₂O₃-SiO₂ catalysts with various SiO₂ contents were prepared via coprecipitation on the surface of foam ceramics. We investigated the effect of SiO₂ incorporation on the physical and chemical properties of the catalysts, such as specific surface area, pore structure, number of acidic sites, metal–support interactions, and catalytic activity. The addition of Si was found to weaken the metal–support interactions, facilitate the reduction of PdO, provide more metal sites, and increase the catalytic efficiency of catalyst. The effects of temperature and pressure on the hydrogenation reaction were also investigated, and under optimal reaction conditions, product yields of up to 85.53 % were achieved. This study offers a novel approach for the catalytic hydrogenation of ethyl nicotinate using carrier-modified metal–acid catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114785"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Application of a carveol dehydrogenase from Klebsiella sp. O852 immobilized on magnetic gel for carvone production","authors":"Yingjie Feng ,&nbsp;Guoguo Wang ,&nbsp;Ting Zhang ,&nbsp;Tingting Zhang ,&nbsp;Zhirou Duan ,&nbsp;Jingyue Wang ,&nbsp;Fengyang Zheng ,&nbsp;Wenzhao Liu ,&nbsp;Lulu Zhang ,&nbsp;Jinchu Yang","doi":"10.1016/j.mcat.2024.114802","DOIUrl":"10.1016/j.mcat.2024.114802","url":null,"abstract":"<div><div>In this study, magnetic gel-embedded immobilized carveol dehydrogenase (Fe₃O₄@Gel@PEI@KlebADH1) was prepared and characterized by fourier transform infrared spectroscopy, scanning electron microscopy and vibrating sample magnetometer. The thermal and pH stabilities, storage stability, and kinetic parameters of Fe₃O₄@Gel@PEI@KlebADH1 compared to that of free KlebADH1 were investigated. Obtained results revealed that the Fe₃O₄@Gel@PEI@KlebADH1 exhibited enhanced stability and catalytic activity, with a superior thermal stability and broader pH range compared to free KlebADH1. After 8 days of storage, immobilized KlebADH1 still retained 69.60 % and 50.37 % of its initial activity at 4 °C and 30 °C, respectively, whereas free KlebADH1 merely retained 17.18 % and 1.97 % of its initial activity. Additionally, after 5 cycles of reuse, Fe₃O₄@Gel@PEI@KlebADH1 still maintained over 60 % of its initial activity, indicating its high reusability. Furthermore, carvone was produced using the Fe₃O₄@Gel@PEI@KlebADH1 as catalyst, and after optimization, the carvone yield reached 8.91 mM using 90 μg/mL Fe₃O₄@Gel@PEI@KlebADH1, 12 mM carveol and 2 mM NADP⁺at 40 °C for 12 h This study identified the potential applications of magnetic gel-embedded immobilized KlebADH1 for the production of carvone.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114802"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Three-liquid-phase system: A highly efficient, enantioselective, and enzyme-recoverable platform for enzymatic chiral resolution reaction","authors":"Jinfen Su ,&nbsp;Wei Zou ,&nbsp;Anwei Xiao ,&nbsp;Qian Liang ,&nbsp;Huayong Chen ,&nbsp;Yonghua Wang ,&nbsp;Bo Yang ,&nbsp;Zhigang Li","doi":"10.1016/j.mcat.2024.114722","DOIUrl":"10.1016/j.mcat.2024.114722","url":null,"abstract":"<div><div>Enzymatic resolution of chiral secondary alcohols has attracted wide attention due to its low cost and environmental pollution as well as mild environmental requirements. However, in the traditional enzymatic reaction system, its application is greatly limited by the low enzymatic catalytic efficiency and enantioselectivity, as well as difficulty in reusing enzymes. Therefore, it is urgent to develop novel enzymatic chiral resolution systems that can overcome these drawbacks. The study assessed the use of a three-liquid-phase system (TLPS) as a novel enzymatic reaction and separation system for the enzymatic chiral resolution of racemic 1-(4-methoxyphenyl) ethanol acetate. Among the systems tested, polymer/salt TLPSs presented promising potential for practical use with superior catalytic efficiency, 10-fold increase in enantiomeric ratio, and 36 % enhancement in hydrolysis efficiency, especially for PEG600/Na₂SO₄ TLPS in comparison with the O/W system. The partition coefficient of the product between the substrate-enriched and product-enriched phases also decreased by more than half for the PEG600/Na₂SO₄ TPLS when compared with the O/W system, and this ensured improved separation of the products from the substrate. Droplet size distribution and microstructure analysis further indicated that the TLPS provided a new phase-transfer catalytic interface with large interfacial reaction area, which was a plausible reason for the enhanced catalytic efficiency. Furthermore, the enzymes that are highly enriched in the middle phase could also be reused, at least for eight rounds without significant loss in enantioselectivity and catalytic efficiency. The high reusability of the enzyme, in addition to promising applicability to different reaction systems were also demonstrated, suggesting the potential application of the TLPS for effective interfacial selective enzymatic catalysis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114722"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146954","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Key engineering criteria for developing next-generation catalysts in advanced Haber–Bosch ammonia synthesis process: From laboratory studies to commercialization","authors":"Kyungho Lee,&nbsp;Hyung Chul Yoon,&nbsp;Sun Hyung Kim,&nbsp;Joonmok Shim,&nbsp;Jae Hyung Kim,&nbsp;Taek-Seung Kim","doi":"10.1016/j.mcat.2024.114781","DOIUrl":"10.1016/j.mcat.2024.114781","url":null,"abstract":"<div><div>Commercializing a catalyst developed in the laboratory is the aspiration of every catalyst researcher, but this step is highly challenging. This <em>Perspective</em> outlines the basic engineering criteria for developing next-generation catalysts capable of meeting the increasing global demand for renewable, carbon-free ammonia (NH₃). A range of key technical and economic factors, extending from active site-scale considerations to process-scale viewpoints are presented. These are operation conditions, activity, long-term stability, formability, and marketability, and their quantitative criteria are proposed to ensure the practicality of the catalyst product. By addressing these interconnected criteria, this <em>Perspective</em> aims to bridge the gap between innovation in laboratory and industrial application, paving the way for a valuable future in catalyst research and development.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114781"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}