Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114765
Kaiyun Lu , Mingxiu Cao , Yuxin Du , Hao Huang , Wenjie Xiang , Guangbo Liu , Jifan Li , Chun-Ling Liu , Noritatsu Tsubaki , Wen-Sheng Dong
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 Hδ− species, consequently achieving excellent catalytic performance for hydrogenolysis of 5-HMF to 2,5-DMF.
{"title":"ZrO2 stablishing CoO facilitates hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran","authors":"Kaiyun Lu , Mingxiu Cao , Yuxin Du , Hao Huang , Wenjie Xiang , Guangbo Liu , Jifan Li , Chun-Ling Liu , Noritatsu Tsubaki , 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 ZrO<sub>2</sub> 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 2ZrO<sub>2</sub>-Co/Al<sub>2</sub>O<sub>3</sub> shows great catalytic performance and good stability, which gives a high 2,5-DMF yield of up to 97.3 %. The addition of ZrO<sub>2</sub> stablishes the metastable state CoO species, which cooperate with suitable oxygen vacancies and enhance the adsorption of 5-HMF and heterolytic dissociation of H<sub>2</sub> to generate highly active H<sup>δ−</sup> 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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114782
Takumi Nakamura, Rin Ito, Hideki Sugimoto, Shinobu Itoh
Catalytic activities of the cobalt(II) complexes supported by tripodal N4-tetradentate ligands have been examined in the alkane hydroxylation reaction by m-CPBA (m-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 = m-chlorophenyl)) derived from m-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 (FeII, NiII, and CuII) support this mechanism.
{"title":"Alkane hydroxylation by m-CPBA catalyzed by Co(II)-complexes","authors":"Takumi Nakamura, Rin Ito, Hideki Sugimoto, 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 N<sub>4</sub>-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<sup>II</sup>, Ni<sup>II</sup>, and Cu<sup>II</sup>) 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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114762
Ilaria Barlocco , Stefano Cattaneo , Silvio Bellomi , Marta Stucchi , Valentina Pifferi , Juan J. Delgado , Xiaowei Chen , Luigi Falciola , Laura Prati , Alberto Villa
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.
{"title":"Influence of the Au-Ag morphology in the electrocatalytic reduction of organic halides","authors":"Ilaria Barlocco , Stefano Cattaneo , Silvio Bellomi , Marta Stucchi , Valentina Pifferi , Juan J. Delgado , Xiaowei Chen , Luigi Falciola , Laura Prati , 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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114785
Fuxin Liang , Yulin Wei , Yuhang Du , Fan Yang , Zhe Pang , Haochen Dang , Junyan Wu , Sai Huang , Honglei Wang , Qinggang Li , Chao Wu , Zhi Wang , Guopu Shi
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.
{"title":"Coating-modified foam ceramic catalysts for ethyl nicotinate hydrogenation","authors":"Fuxin Liang , Yulin Wei , Yuhang Du , Fan Yang , Zhe Pang , Haochen Dang , Junyan Wu , Sai Huang , Honglei Wang , Qinggang Li , Chao Wu , Zhi Wang , 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/Al<sub>2</sub>O<sub>3</sub>-SiO<sub>2</sub> catalysts with various SiO<sub>2</sub> contents were prepared via coprecipitation on the surface of foam ceramics. We investigated the effect of SiO<sub>2</sub> 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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114802
Yingjie Feng , Guoguo Wang , Ting Zhang , Tingting Zhang , Zhirou Duan , Jingyue Wang , Fengyang Zheng , Wenzhao Liu , Lulu Zhang , Jinchu Yang
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.
{"title":"Application of a carveol dehydrogenase from Klebsiella sp. O852 immobilized on magnetic gel for carvone production","authors":"Yingjie Feng , Guoguo Wang , Ting Zhang , Tingting Zhang , Zhirou Duan , Jingyue Wang , Fengyang Zheng , Wenzhao Liu , Lulu Zhang , 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 (Fe<sub>3</sub>O<sub>4</sub>@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 Fe<sub>3</sub>O<sub>4</sub>@Gel@PEI@KlebADH1 compared to that of free KlebADH1 were investigated. Obtained results revealed that the Fe<sub>3</sub>O<sub>4</sub>@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, Fe<sub>3</sub>O<sub>4</sub>@Gel@PEI@KlebADH1 still maintained over 60 % of its initial activity, indicating its high reusability. Furthermore, carvone was produced using the Fe<sub>3</sub>O<sub>4</sub>@Gel@PEI@KlebADH1 as catalyst, and after optimization, the carvone yield reached 8.91 mM using 90 μg/mL Fe<sub>3</sub>O<sub>4</sub>@Gel@PEI@KlebADH1, 12 mM carveol and 2 mM NADP<sup>+</sup>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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114722
Jinfen Su , Wei Zou , Anwei Xiao , Qian Liang , Huayong Chen , Yonghua Wang , Bo Yang , Zhigang Li
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.
{"title":"Three-liquid-phase system: A highly efficient, enantioselective, and enzyme-recoverable platform for enzymatic chiral resolution reaction","authors":"Jinfen Su , Wei Zou , Anwei Xiao , Qian Liang , Huayong Chen , Yonghua Wang , Bo Yang , 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/Na<sub>2</sub>SO<sub>4</sub> 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/Na<sub>2</sub>SO<sub>4</sub> 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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114781
Kyungho Lee, Hyung Chul Yoon, Sun Hyung Kim, Joonmok Shim, Jae Hyung Kim, Taek-Seung Kim
Commercializing a catalyst developed in the laboratory is the aspiration of every catalyst researcher, but this step is highly challenging. This Perspective 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 Perspective aims to bridge the gap between innovation in laboratory and industrial application, paving the way for a valuable future in catalyst research and development.
{"title":"Key engineering criteria for developing next-generation catalysts in advanced Haber–Bosch ammonia synthesis process: From laboratory studies to commercialization","authors":"Kyungho Lee, Hyung Chul Yoon, Sun Hyung Kim, Joonmok Shim, Jae Hyung Kim, 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 (NH<sub>3</sub>). 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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114793
Yiheng Huang, Jiarui Wang, Hui Hu, Zhengping Qiao, Yan Li, Chengxin Wang
The local coordination environment regulation of M-N4-C type single-atom catalysts (SACs) by introducing heteroatom (X = B, C, O, P, S) have attracted significant attention for their controllable properties and fantastic catalytic activity in the electrocatalytic CO2 reduction reaction (CO2RR). However, the numerous possible configurations of M-NX-C result in excessive computational costs. Herein, we tackled that issue via machine learning-assisted density functional theory (DFT) calculations outperforming the conventional time-consuming high-throughput screening. Initially, DFT calculations demonstrate that the adsorption energy of CO can serve as a high-efficiency descriptor to predict the CO2RR performance of M-NX-C SACs. Then, using this descriptor we screened quite a few superior SACs toward CO2RR using machine learning model of extreme gradient boosting (XGBoost) which can predict the catalytic performance of SACs with various parameters regarding local structures of metal centers. Those screened SACs of PtN3B, RhN4, TiN2P2-ortho, FeN2O2-para (experimentally proven recently), CoN4 (experimentally proven), NiN3B and CuN3B possess quite competitive limiting potentials, which have also been further validated by DFT calculations, exhibiting a faithful predictive ability of the XGBoost model. Besides, effective regulation strategies of local environments for promising CO2RR performance were proposed for the most widely investigated M-N4-C (M = Fe, Co, Ni and Cu) SACs. This work is significant for understanding the mechanism of the nearest neighbor regulation of M-N4-C SACs for CO2RR and guiding the future experimental synthesis of them.
{"title":"Heteroatom-doped M-N4-C Single-atom catalysts towards electrochemical reactions of CO2: A machine learning-assisted DFT study","authors":"Yiheng Huang, Jiarui Wang, Hui Hu, Zhengping Qiao, Yan Li, Chengxin Wang","doi":"10.1016/j.mcat.2024.114793","DOIUrl":"10.1016/j.mcat.2024.114793","url":null,"abstract":"<div><div>The local coordination environment regulation of M-N<sub>4</sub>-C type single-atom catalysts (SACs) by introducing heteroatom (X = B, C, O, P, S) have attracted significant attention for their controllable properties and fantastic catalytic activity in the electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). However, the numerous possible configurations of M-NX-C result in excessive computational costs. Herein, we tackled that issue via machine learning-assisted density functional theory (DFT) calculations outperforming the conventional time-consuming high-throughput screening. Initially, DFT calculations demonstrate that the adsorption energy of CO can serve as a high-efficiency descriptor to predict the CO<sub>2</sub>RR performance of M-NX-C SACs. Then, using this descriptor we screened quite a few superior SACs toward CO<sub>2</sub>RR using machine learning model of extreme gradient boosting (XGBoost) which can predict the catalytic performance of SACs with various parameters regarding local structures of metal centers. Those screened SACs of PtN<sub>3</sub>B, RhN<sub>4</sub>, TiN<sub>2</sub>P<sub>2</sub>-ortho, FeN<sub>2</sub>O<sub>2</sub>-para (experimentally proven recently), CoN<sub>4</sub> (experimentally proven), NiN<sub>3</sub>B and CuN<sub>3</sub>B possess quite competitive limiting potentials, which have also been further validated by DFT calculations, exhibiting a faithful predictive ability of the XGBoost model. Besides, effective regulation strategies of local environments for promising CO<sub>2</sub>RR performance were proposed for the most widely investigated M-N<sub>4</sub>-C (M = Fe, Co, Ni and Cu) SACs. This work is significant for understanding the mechanism of the nearest neighbor regulation of M-N<sub>4</sub>-C SACs for CO<sub>2</sub>RR and guiding the future experimental synthesis of them.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114793"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146969","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}
Hydrogen is the lightest element and is strongly affected by nuclear quantum effects. We have developed the Hessian calculation with the combined plane wave and localized basis sets (CPLB) method to efficiently analyze an adsorbed molecule on metal surfaces. To validate the effectiveness of the CPLB Hessian, we conducted test calculations for the H2O dimer and applied it to the surface system of an H2O molecule adsorbed on the Pt(111) surface. The adsorption energy of the H2O molecule without zero-point energy correction is 0.603 eV, while the adsorption energy with ZPE correction is 0.444 eV This suggests that the zero-point energy correction reduces the adsorption energy. We also estimated the adsorption energy of a heavy water D2O molecule as 0.471 eV, which is consistent with the experimental trends. Such vibrational estimation with the CPLB method enables us to perform efficient low-cost calculations, even in large-scale systems such as metal surfaces.
{"title":"Development of Hessian calculation using the combined plane wave and localized basis sets method and its application to adsorption of a water molecule on Pt(111) surface","authors":"Hiroki Sakagami , Makito Takagi , Takayoshi Ishimoto , Tomomi Shimazaki , Masanori Tachikawa","doi":"10.1016/j.mcat.2024.114791","DOIUrl":"10.1016/j.mcat.2024.114791","url":null,"abstract":"<div><div>Hydrogen is the lightest element and is strongly affected by nuclear quantum effects. We have developed the Hessian calculation with the combined plane wave and localized basis sets (CPLB) method to efficiently analyze an adsorbed molecule on metal surfaces. To validate the effectiveness of the CPLB Hessian, we conducted test calculations for the H<sub>2</sub>O dimer and applied it to the surface system of an H<sub>2</sub>O molecule adsorbed on the Pt(111) surface. The adsorption energy of the H<sub>2</sub>O molecule without zero-point energy correction is 0.603 eV, while the adsorption energy with ZPE correction is 0.444 eV This suggests that the zero-point energy correction reduces the adsorption energy. We also estimated the adsorption energy of a heavy water D<sub>2</sub>O molecule as 0.471 eV, which is consistent with the experimental trends. Such vibrational estimation with the CPLB method enables us to perform efficient low-cost calculations, even in large-scale systems such as metal surfaces.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114791"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147608","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}
Pub Date : 2025-02-01DOI: 10.1016/j.mcat.2024.114783
Huijia Chen , Shun Liu , Jin Wang, Sunying Zhou, Yan Chen, Fang Ke, Xiuzhi Xu
Graphitic Carbon Nitride (g-C3N4) has emerged as one of the desired materials in photocatalysis due to its visible-light activity and its unique layered structure. However, the efficiency of bare g-C3N4 as a photocatalyst is limited by the high recombination rate of photogenerated electron-hole pairs. To improve photon utilization and extend the carrier lifetime in the photocatalytic reaction, we composite Fe2O3 with g-C3N4, greatly enhancing the photocatalytic activity. Fe2O3@C3N4 achieves CH functionalization via the Minisci reaction, selectively cleaving the CN bond in phenylhydrazine to form phenyl radicals, followed by nucleophilic addition reactions with protonated quinoline radicals. Notably, the catalyst exhibits high efficiency and excellent yields in large-scale reactions. Moreover, it can be easily recovered by centrifugation and reused at least six times without significant loss of catalytic performance.
{"title":"Unlocking the potential of Minisci: Aromatisation of nitrogenous heterocycles using recyclable photocatalysts","authors":"Huijia Chen , Shun Liu , Jin Wang, Sunying Zhou, Yan Chen, Fang Ke, Xiuzhi Xu","doi":"10.1016/j.mcat.2024.114783","DOIUrl":"10.1016/j.mcat.2024.114783","url":null,"abstract":"<div><div>Graphitic Carbon Nitride (g-C<sub>3</sub>N<sub>4</sub>) has emerged as one of the desired materials in photocatalysis due to its visible-light activity and its unique layered structure. However, the efficiency of bare g-C<sub>3</sub>N<sub>4</sub> as a photocatalyst is limited by the high recombination rate of photogenerated electron-hole pairs. To improve photon utilization and extend the carrier lifetime in the photocatalytic reaction, we composite Fe<sub>2</sub>O<sub>3</sub> with g-C<sub>3</sub>N<sub>4</sub>, greatly enhancing the photocatalytic activity. Fe<sub>2</sub>O<sub>3</sub>@C<sub>3</sub>N<sub>4</sub> achieves C<img>H functionalization via the Minisci reaction, selectively cleaving the C<img>N bond in phenylhydrazine to form phenyl radicals, followed by nucleophilic addition reactions with protonated quinoline radicals. Notably, the catalyst exhibits high efficiency and excellent yields in large-scale reactions. Moreover, it can be easily recovered by centrifugation and reused at least six times without significant loss of catalytic performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114783"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146970","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}
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