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Photocatalytic synthesis of aryltriazenes by CulnS2/K-C3N4 heterojunctions
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114764
Ge Gao , Chuan-Jie Han , Qian-Hui Liu , Li-Ping Mo , Zhan-Hui Zhang
An efficient protocol for the synthesis of triazenes has been established, utilising a Z-scheme CuInS₂/K-C₃N₄ heterojunction as a photocatalyst in cyclopentyl methyl ether. This method enables the synthesis of a wide range of aryl triazenes with excellent yields and remarkable functional group tolerance, utilizing diazonium salts and secondary amines as substrates. The feasibility and robustness of this approach are further underscored by the CuInS₂/K-C₃N₄ photocatalyst's ability to be recycled and reused multiple times without significant loss of catalytic activity.
{"title":"Photocatalytic synthesis of aryltriazenes by CulnS2/K-C3N4 heterojunctions","authors":"Ge Gao ,&nbsp;Chuan-Jie Han ,&nbsp;Qian-Hui Liu ,&nbsp;Li-Ping Mo ,&nbsp;Zhan-Hui Zhang","doi":"10.1016/j.mcat.2024.114764","DOIUrl":"10.1016/j.mcat.2024.114764","url":null,"abstract":"<div><div>An efficient protocol for the synthesis of triazenes has been established, utilising a Z-scheme CuInS₂/K-C₃N₄ heterojunction as a photocatalyst in cyclopentyl methyl ether. This method enables the synthesis of a wide range of aryl triazenes with excellent yields and remarkable functional group tolerance, utilizing diazonium salts and secondary amines as substrates. The feasibility and robustness of this approach are further underscored by the CuInS₂/K-C₃N₄ photocatalyst's ability to be recycled and reused multiple times without significant loss of catalytic activity.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114764"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146887","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}
引用次数: 0
A tetrameric double peroxyl bonds-bridged Zr-substituted phosphotungstate with good catalytic oxidation activity for sulfides
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114786
Dongsheng Yang , Miao Wang , Lin Sun , Pengtao Ma
Exploring an effective catalyst to catalytically oxidize sulfides to the corresponding sulfoxides or sulfones is of crucial importance not only for environmental protection, but also for the synthesis of high-value chemicals. Herein, a neoteric tetrameric double peroxyl bonds-bridged Zr-substituted phosphotungstate, K8Na19.5H0.5[Zr2(O2)2(β-PW10O38)]4·68H2O (1), has been successfully synthesized by a conventional aqueous method. Compound 1 is consisted of four [β-PW10O38]11− subunits, where every two [β-PW10O38]11− subunits are bridged by two Zr4+ ions via double peroxyl bonds to form a square-shaped structure. Moreover, compound 1 was selected as an effective catalyst for the catalytic oxidation of sulfides to sulfoxides or sulfones owing to the good catalytic property of POMs. As expected, 1 exhibits good performance in catalytic oxidation of sulfides to the responding sulfoxides or sulfones.
{"title":"A tetrameric double peroxyl bonds-bridged Zr-substituted phosphotungstate with good catalytic oxidation activity for sulfides","authors":"Dongsheng Yang ,&nbsp;Miao Wang ,&nbsp;Lin Sun ,&nbsp;Pengtao Ma","doi":"10.1016/j.mcat.2024.114786","DOIUrl":"10.1016/j.mcat.2024.114786","url":null,"abstract":"<div><div>Exploring an effective catalyst to catalytically oxidize sulfides to the corresponding sulfoxides or sulfones is of crucial importance not only for environmental protection, but also for the synthesis of high-value chemicals. Herein, a neoteric tetrameric double peroxyl bonds-bridged Zr-substituted phosphotungstate, K<sub>8</sub>Na<sub>19.5</sub>H<sub>0.5</sub>[Zr<sub>2</sub>(O<sub>2</sub>)<sub>2</sub>(β-PW<sub>10</sub>O<sub>38</sub>)]<sub>4</sub>·68H<sub>2</sub>O (<strong>1</strong>), has been successfully synthesized by a conventional aqueous method. Compound <strong>1</strong> is consisted of four [β-PW<sub>10</sub>O<sub>38</sub>]<sup>11−</sup> subunits, where every two [β-PW<sub>10</sub>O<sub>38</sub>]<sup>11−</sup> subunits are bridged by two Zr<sup>4+</sup> ions via double peroxyl bonds to form a square-shaped structure. Moreover, compound <strong>1</strong> was selected as an effective catalyst for the catalytic oxidation of sulfides to sulfoxides or sulfones owing to the good catalytic property of POMs. As expected, <strong>1</strong> exhibits good performance in catalytic oxidation of sulfides to the responding sulfoxides or sulfones.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114786"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146965","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}
引用次数: 0
Silica-supported Pt-In intermetallic alloy for low-temperature reverse water–gas shift reaction
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2025.114890
Jie Zhao, Ruixue Bao, Ruru Sun, Xiaolong Zhang, Tao Zhang, Chuanyi Wang
The reverse water–gas shift reaction (RWGS) has been regarded as an important route for CO2 utilization. Because the RWGS reaction is a mildly endothermic and competitive reaction with CO2 methanation, it is necessary to explore catalysts with high activity and selectivity at low reaction temperatures. Herein, we investigate the catalytic characteristic of silica-supported Pt-In alloy for RWGS reaction by comparing it with silica-supported Pt and In2O3-modified Pt. It is found that Pt-In/SiO2 exhibits significantly higher activity than Pt/SiO2 at reaction temperatures from 140 to 200 °C, and equivalent activities appear at 240 °C. Further raising the temperatures, the activity of Pt/SiO2 increases rapidly. CO selectivity over Pt-In/SiO2 is close to 100 % and higher than Pt/SiO2 (∼95 %) under dynamic reaction mode, being attributed to the effective expelling of CO away from the Pt-In surface by CO2 molecules and the decreased atomic hydrogen supply. Moreover, the formate and the redox pathways were followed over Pt-In/SiO2 and Pt/SiO2, respectively. Except for higher activity and selectivity to CO, In2O3-modified Pt exhibits the same catalytic pathways as Pt/SiO2. The present work supplied a guide to explore efficient catalysts for RWGS reaction at low reaction temperatures.
{"title":"Silica-supported Pt-In intermetallic alloy for low-temperature reverse water–gas shift reaction","authors":"Jie Zhao,&nbsp;Ruixue Bao,&nbsp;Ruru Sun,&nbsp;Xiaolong Zhang,&nbsp;Tao Zhang,&nbsp;Chuanyi Wang","doi":"10.1016/j.mcat.2025.114890","DOIUrl":"10.1016/j.mcat.2025.114890","url":null,"abstract":"<div><div>The reverse water–gas shift reaction (RWGS) has been regarded as an important route for CO<sub>2</sub> utilization. Because the RWGS reaction is a mildly endothermic and competitive reaction with CO<sub>2</sub> methanation, it is necessary to explore catalysts with high activity and selectivity at low reaction temperatures. Herein, we investigate the catalytic characteristic of silica-supported Pt-In alloy for RWGS reaction by comparing it with silica-supported Pt and In<sub>2</sub>O<sub>3</sub>-modified Pt. It is found that Pt-In/SiO<sub>2</sub> exhibits significantly higher activity than Pt/SiO<sub>2</sub> at reaction temperatures from 140 to 200 °C, and equivalent activities appear at 240 °C. Further raising the temperatures, the activity of Pt/SiO<sub>2</sub> increases rapidly. CO selectivity over Pt-In/SiO<sub>2</sub> is close to 100 % and higher than Pt/SiO<sub>2</sub> (∼95 %) under dynamic reaction mode, being attributed to the effective expelling of CO away from the Pt-In surface by CO<sub>2</sub> molecules and the decreased atomic hydrogen supply. Moreover, the formate and the redox pathways were followed over Pt-In/SiO<sub>2</sub> and Pt/SiO<sub>2</sub>, respectively. Except for higher activity and selectivity to CO, In<sub>2</sub>O<sub>3</sub>-modified Pt exhibits the same catalytic pathways as Pt/SiO<sub>2</sub>. The present work supplied a guide to explore efficient catalysts for RWGS reaction at low reaction temperatures.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"574 ","pages":"Article 114890"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143152951","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}
引用次数: 0
Fe-modified Cu/TiO2 catalyst with anti-Pb poisoning performance for the synergistic catalysis of NH3-SCR and CO oxidation
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114773
Yang-wen Wu, Zheng-long Wu, Hai-yuan Zhao, Xu Su, Ji-hong Li, Qiang Lu
Nitrogen oxides (NOx) and carbon monoxide (CO) are two major pollutants in industrial flue gas. Currently, ammonia selective catalytic reduction (NH3-SCR) and CO oxidation catalysts are susceptible to heavy metal impurities such as Pb, which leads to a reduction in catalytic activities. In this study, an excellent anti-Pb poisoning Fe-enhanced Cu/TiO2 catalyst was prepared for the synergistic control of NO and CO with maximum 91.2 % and 99 % conversion ratios at 275 °C. The active components of the modified catalyst were well dispersed on the TiO2. The doping of Fe alleviated the surface aggregation caused by Pb, while the pore size was decreased and the specific surface area was increased. Synergistic interaction between Cu and Fe produced more variable valence states, leading to highly active chemisorbed oxygen and oxygen vacancies, which were beneficial for the NO and CO removal. Furthermore, after Fe loading more acidic sites were retained on the catalyst surface, which improved the oxidation–reduction characteristics of the catalyst. This research presents a viable approach for designing efficient catalyst for the concurrent removal of NO and CO from industrial emissions while demonstrating great resistance to Pb-poisoning.
{"title":"Fe-modified Cu/TiO2 catalyst with anti-Pb poisoning performance for the synergistic catalysis of NH3-SCR and CO oxidation","authors":"Yang-wen Wu,&nbsp;Zheng-long Wu,&nbsp;Hai-yuan Zhao,&nbsp;Xu Su,&nbsp;Ji-hong Li,&nbsp;Qiang Lu","doi":"10.1016/j.mcat.2024.114773","DOIUrl":"10.1016/j.mcat.2024.114773","url":null,"abstract":"<div><div>Nitrogen oxides (NO<em><sub>x</sub></em>) and carbon monoxide (CO) are two major pollutants in industrial flue gas. Currently, ammonia selective catalytic reduction (NH<sub>3</sub>-SCR) and CO oxidation catalysts are susceptible to heavy metal impurities such as Pb, which leads to a reduction in catalytic activities. In this study, an excellent anti-Pb poisoning Fe-enhanced Cu/TiO<sub>2</sub> catalyst was prepared for the synergistic control of NO and CO with maximum 91.2 % and 99 % conversion ratios at 275 °C. The active components of the modified catalyst were well dispersed on the TiO<sub>2</sub>. The doping of Fe alleviated the surface aggregation caused by Pb, while the pore size was decreased and the specific surface area was increased. Synergistic interaction between Cu and Fe produced more variable valence states, leading to highly active chemisorbed oxygen and oxygen vacancies, which were beneficial for the NO and CO removal. Furthermore, after Fe loading more acidic sites were retained on the catalyst surface, which improved the oxidation–reduction characteristics of the catalyst. This research presents a viable approach for designing efficient catalyst for the concurrent removal of NO and CO from industrial emissions while demonstrating great resistance to Pb-poisoning.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114773"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146286","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}
引用次数: 0
Robust tetrazole-linked bimetallic Ru(II) complexes as catalysts for base-free acceptor-less double dehydrogenation of primary amines to nitriles under milder conditions
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114797
Nimesh R. Chauhan , Sakshi , Angshuman Roy Choudhury , Komal M. Vyas
The catalytic double dehydrogenation (DDH) of primary amines is a clean and efficient method over aerobic oxidation. Further, the utilization of bimetallic catalytic system for DDH has proven to be more efficient than its monometallic counterpart. However, its large scale adoption for industrial application is limited owing to the usage of expensive and environmentally adverse catalytic conditions. In this context, the present study describes the first example of tetrazole-derived two bimetallic Ru(II)-arene complexes [(η6-p-cymene)2Ru2Cl3(L1)] [Ru-1] and [(η6-benzene)2Ru2Cl3(L1)] [Ru-2] (where, L1 = 4-(1H-tetrazole-5yl)benzoic acid) for acceptor-less double dehydrogenation of primary amines under oxidant and base free conditions. The results suggest that the electron rich [Ru-1] has outperformed due to its high solubility, high electron density and more charge separation as compared to [Ru-2]. The mechanistic studies reveal that electrophilic centre of [Ru-1] easily associates with substrate, whereas nucleophilic metal centre abstracts β-hydrogen of primary amine via thermodynamically more favourable six-membered transition state as compared to traditional four membered transition state in monometallic system. Further, the catalytic investigation proves that electron rich aromatic primary amines and aliphatic amines are more powerful than bidentate substrates which deactivate the catalyst suggesting the bimetallic dehydrogenation pathway for primary amines. Overall, this research opens the possibility of exploring tetrazole linked bimetallic complexes as an industry efficient solution for transition of primary amines to nitriles.
{"title":"Robust tetrazole-linked bimetallic Ru(II) complexes as catalysts for base-free acceptor-less double dehydrogenation of primary amines to nitriles under milder conditions","authors":"Nimesh R. Chauhan ,&nbsp;Sakshi ,&nbsp;Angshuman Roy Choudhury ,&nbsp;Komal M. Vyas","doi":"10.1016/j.mcat.2024.114797","DOIUrl":"10.1016/j.mcat.2024.114797","url":null,"abstract":"<div><div>The catalytic double dehydrogenation (DDH) of primary amines is a clean and efficient method over aerobic oxidation. Further, the utilization of bimetallic catalytic system for DDH has proven to be more efficient than its monometallic counterpart. However, its large scale adoption for industrial application is limited owing to the usage of expensive and environmentally adverse catalytic conditions. In this context, the present study describes the first example of tetrazole-derived two bimetallic Ru(II)-arene complexes [(η<sup>6</sup>-<em>p</em>-cymene)<sub>2</sub>Ru<sub>2</sub>Cl<sub>3</sub>(L1)] <strong>[Ru-1]</strong> and [(η<sup>6</sup>-benzene)<sub>2</sub>Ru<sub>2</sub>Cl<sub>3</sub>(L1)] <strong>[Ru-2]</strong> (where, L1 = 4-(1<em>H</em>-tetrazole-5yl)benzoic acid) for acceptor-less double dehydrogenation of primary amines under oxidant and base free conditions. The results suggest that the electron rich <strong>[Ru-1]</strong> has outperformed due to its high solubility, high electron density and more charge separation as compared to <strong>[Ru-2]</strong>. The mechanistic studies reveal that electrophilic centre of <strong>[Ru-1]</strong> easily associates with substrate, whereas nucleophilic metal centre abstracts β-hydrogen of primary amine <em>via</em> thermodynamically more favourable six-membered transition state as compared to traditional four membered transition state in monometallic system. Further, the catalytic investigation proves that electron rich aromatic primary amines and aliphatic amines are more powerful than bidentate substrates which deactivate the catalyst suggesting the bimetallic dehydrogenation pathway for primary amines. Overall, this research opens the possibility of exploring tetrazole linked bimetallic complexes as an industry efficient solution for transition of primary amines to nitriles.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114797"},"PeriodicalIF":3.9,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146958","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}
引用次数: 0
Theoretical insight on the delicate regulation of coordination environments for carbon-nitrogen-supported single-atom metals for OER and ORR
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114784
Xiao-Kuan Wu, Junan Gao, Zhao Hong, Zhigang Lei, Jie Zhang
Carbon-nitrogen-supported single-atom catalysts have significant potential in electrochemistry; however, the real active site TM-Cx-Ny 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-Cx-Ny 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-Cx-Ny 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 (Ne = 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 ηOER/ORR, thus allowing an accurate representation of the activity of various TM-Cx-Ny 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.
{"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><sub>x</sub></em>-N<em><sub>y</sub></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><sub>x</sub></em>-N<em><sub>y</sub></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><sub>x</sub></em>-N<em><sub>y</sub></em> exhibit robust thermodynamic and electrochemical stability. Among these, Ni-C<sub>4</sub>, Co-N<sub>4</sub>, and Rh-N<sub>4</sub> demonstrate the most promising OER and ORR activities. By calculating the modulation interval of intermediate adsorption energies from TM-C<sub>4</sub> to TM-N<sub>4</sub>, it was found that metals with different valence electrons exhibit disparate sensitivities to coordination modulation with Group VIII(II) elements (N<em><sub>e</sub></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<sup>OER/ORR</sup>, thus allowing an accurate representation of the activity of various TM-C<em><sub>x</sub></em>-N<em><sub>y</sub></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}
引用次数: 0
Competitive effects of polymeric ligands molecular weight on the gold colloidal nanocatalysts: Impact of catalysts design and catalytic performance
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114780
Stefano Scurti , Elena Rodríguez-Aguado , Juan Antonio Cecilia , Daniele Caretti , Nikolaos Dimitratos
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 (kapp) decreased, particularly for PEO-based catalysts, where kapp 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.
{"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<sub>app</sub>) decreased, particularly for PEO-based catalysts, where k<sub>app</sub> 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}
引用次数: 0
Rational regulation of efficient nitrogen-bridge heteronuclear metal electrocatalyst for nitrogen fixation
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 10.1016/j.mcat.2024.114794
Shuo Wang, Likai Yan, Zhongmin Su
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.
{"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 N<sub>2</sub> 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-N<sub>4</sub> moieties regulates the interaction between *N<sub>2</sub> intermediates and metal center thus accelerating NRR. The distribution of metal d orbitals can also be used to determine the dominant configuration of N<sub>2</sub> adsorption. Highly efficient and selective BACs for NRR can be screened based on the scaling relationship between the key intermediates (*N<sub>2</sub>H and *NH<sub>2</sub>). 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}
引用次数: 0
ZrO2 stablishing CoO facilitates hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 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 ,&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 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}
引用次数: 0
Alkane hydroxylation by m-CPBA catalyzed by Co(II)-complexes
IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-01 DOI: 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,&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 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}
引用次数: 0
期刊
Molecular Catalysis
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