Pub Date : 2025-04-12DOI: 10.1016/j.jcat.2025.116142
Guangxu Yao, Jin Wan, Yangjun Luo, Dong Liu, Guolong Qiu, Huijuan Zhang, Yu Wang
Strategic localization of catalytically active sites within single-atom catalyst (SAC) architectures represents a pivotal determinant of material performance, particularly in two-dimensional (2D) substrates like MXenes, which offer intricate structural complexity and multifarious anchoring potentialities. Despite the burgeoning interest in non-metallic single-atom catalysts, a comprehensive understanding of site-specific loading mechanisms and their consequential catalytic implications remains substantially unexplored. Herein, we systematically investigate the precise incorporation of economically viable non-metallic elements—tellurium (Te) and arsenic (As)—onto Ti3C2 MXene, a prototypical 2D material characterized by exceptional structural versatility. Our methodology delineates a nuanced approach to controllable single-atom immobilization, strategically differentiating between vacancy-embedded and surface-supported configurations. Through meticulous experimental design, we demonstrate that Te single atoms strategically integrated within titanium vacancies (C-TeSA-T) manifest superior Oxygen Reduction Reaction (ORR) electrocatalytic performance compared to surface-anchored counterparts (W-TeSA-T). Comprehensive characterization revealed remarkable electrocatalytic metrics, including a half-wave potential of 0.88 V vs. RHE and a limiting current density of 5.65 mA/cm2. Synergistic Density Functional Theory (DFT) computations and multi-potential X-ray Photoelectron Spectroscopic (XPS) analyses elucidated the intrinsic mechanistic landscape, conclusively identifying Te single atoms as primary catalytic centers and delineating the rate-determining reaction trajectory. This systematic investigation not only introduces an innovative paradigm for designing cost-effective non-metallic catalysts but also provides fundamental mechanistic insights into the intricate relationship between active site localization and catalytic performance, thereby advancing our fundamental understanding of site-specific catalysis in two-dimensional materials.
{"title":"Position-controlled non-metal single atoms on MXene enable high-performance oxygen reduction electrocatalysis","authors":"Guangxu Yao, Jin Wan, Yangjun Luo, Dong Liu, Guolong Qiu, Huijuan Zhang, Yu Wang","doi":"10.1016/j.jcat.2025.116142","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116142","url":null,"abstract":"Strategic localization of catalytically active sites within single-atom catalyst (SAC) architectures represents a pivotal determinant of material performance, particularly in two-dimensional (2D) substrates like MXenes, which offer intricate structural complexity and multifarious anchoring potentialities. Despite the burgeoning interest in non-metallic single-atom catalysts, a comprehensive understanding of site-specific loading mechanisms and their consequential catalytic implications remains substantially unexplored. Herein, we systematically investigate the precise incorporation of economically viable non-metallic elements—tellurium (Te) and arsenic (As)—onto Ti<sub>3</sub>C<sub>2</sub> MXene, a prototypical 2D material characterized by exceptional structural versatility. Our methodology delineates a nuanced approach to controllable single-atom immobilization, strategically differentiating between vacancy-embedded and surface-supported configurations. Through meticulous experimental design, we demonstrate that Te single atoms strategically integrated within titanium vacancies (C-TeSA-T) manifest superior Oxygen Reduction Reaction (ORR) electrocatalytic performance compared to surface-anchored counterparts (W-TeSA-T). Comprehensive characterization revealed remarkable electrocatalytic metrics, including a half-wave potential of 0.88 V vs. RHE and a limiting current density of 5.65 mA/cm<sup>2</sup>. Synergistic Density Functional Theory (DFT) computations and multi-potential X-ray Photoelectron Spectroscopic (XPS) analyses elucidated the intrinsic mechanistic landscape, conclusively identifying Te single atoms as primary catalytic centers and delineating the rate-determining reaction trajectory. This systematic investigation not only introduces an innovative paradigm for designing cost-effective non-metallic catalysts but also provides fundamental mechanistic insights into the intricate relationship between active site localization and catalytic performance, thereby advancing our fundamental understanding of site-specific catalysis in two-dimensional materials.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"14 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-12DOI: 10.1016/j.jcat.2025.116143
Loraine Soumoy, Anthony Morena, Marco Armandi, Sonia Fiorilli, Luca Fusaro, Damien P. Debecker, Carmela Aprile
Ga-doped hollow silica nanosphere and nanotubes were synthetized using a soft template sol–gel method. The low dimensional morphologies (0D or 1D) were obtained by simply adjusting the stirring speed during the synthesis procedure. The two materials were fully characterized using different techniques such as ssNMR, N2 physisorption, XRD, TEM or ICP-OES. The influence of the calcination temperature on the coordination environment of gallium as well as the accessibility of the gallium active sites was proved via 71Ga ssNMR. The acid features of the solids were studied via a combined approach based on FT-IR of adsorbed ammonia and 31P ssNMR using trimethylphosphine as a probe molecule. The latter technique allows unveiling a higher Brønsted/Lewis acid sites ratio of Ga-nanospheres as compared to Ga-nanotubes, probably as a consequence of the more defective spherical shell. Both nanostructures were tested for the conversion of glycerol to solketal. Ga-nanospheres revealed improved catalytic performance in comparison with the corresponding nanotubes and displayed outstanding activity with respect to other solid catalysts reported in the literature and tested under the same reaction conditions. Moreover, they proved to be stable and reusable in multiple cycles. The E-factor calculated under the best condition was below 1 thus proving the sustainability of the process.
{"title":"Gallium based hollow silica nanospheres for the acid-catalyzed up-grading of glycerol: Enhanced activity disclosed via an in-depth nuclear magnetic resonance approach","authors":"Loraine Soumoy, Anthony Morena, Marco Armandi, Sonia Fiorilli, Luca Fusaro, Damien P. Debecker, Carmela Aprile","doi":"10.1016/j.jcat.2025.116143","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116143","url":null,"abstract":"Ga-doped hollow silica nanosphere and nanotubes were synthetized using a soft template sol–gel method. The low dimensional morphologies (0D or 1D) were obtained by simply adjusting the stirring speed during the synthesis procedure. The two materials were fully characterized using different techniques such as ssNMR, N<sub>2</sub> physisorption, XRD, TEM or ICP-OES. The influence of the calcination temperature on the coordination environment of gallium as well as the accessibility of the gallium active sites was proved via <sup>71</sup>Ga ssNMR. The acid features of the solids were studied via a combined approach based on FT-IR of adsorbed ammonia and <sup>31</sup>P ssNMR using trimethylphosphine as a probe molecule. The latter technique allows unveiling a higher Brønsted/Lewis acid sites ratio of Ga-nanospheres as compared to Ga-nanotubes, probably as a consequence of the more defective spherical shell. Both nanostructures were tested for the conversion of glycerol to solketal. Ga-nanospheres revealed improved catalytic performance in comparison with the corresponding nanotubes and displayed outstanding activity with respect to other solid catalysts reported in the literature and tested under the same reaction conditions. Moreover, they proved to be stable and reusable in multiple cycles. The E-factor calculated under the best condition was below 1 thus proving the sustainability of the process.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"218 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822931","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-11DOI: 10.1016/j.jcat.2025.116139
Yuxing Lin , Weihua Yang , Meijie Wang , Lei Li , Yameng Li , Xing Chen , Rao Huang , Yuhua Wen
The design of multiple types of active sites with cooperative functions on catalyst surface holds great promise for urea synthesis, yet forming these specific sites and ensuring their functionality remain a prominent challenge. Here, we propose two types of Mo2C grain boundaries (GBs) that feature intrinsic cooperative active sites, facilitating the coupling of C and N species and achieving efficient urea synthesis. By density-functional theory (DFT) calculations, we verify that positively charged Mo atoms on the GBs exhibit high adsorption and reduction activity for CO2, whereas adjacent Mo atoms contribute to the activation of N2 or NO. The cooperative effects of these active sites enables C-N coupling to proceed spontaneously on the GBs with ultralow limiting potentials (−0.24 ∼ −0.42 V). Furthermore, analysis of the competing hydrogen evolution reaction and nitrogen reduction reaction confirms the high selectivity to generate urea on Mo2C GBs. Our work demonstrates GB engineering as a promising strategy for urea generation through the synergistic cooperation between multiple active sites, thus paving the way towards the rational design of effective catalysts for urea electrosynthesis.
{"title":"Electrochemical synthesis of urea at cooperative active sites on Mo2C grain boundary","authors":"Yuxing Lin , Weihua Yang , Meijie Wang , Lei Li , Yameng Li , Xing Chen , Rao Huang , Yuhua Wen","doi":"10.1016/j.jcat.2025.116139","DOIUrl":"10.1016/j.jcat.2025.116139","url":null,"abstract":"<div><div>The design of multiple types of active sites with cooperative functions on catalyst surface holds great promise for urea synthesis, yet forming these specific sites and ensuring their functionality remain a prominent challenge. Here, we propose two types of Mo<sub>2</sub>C grain boundaries (GBs) that feature intrinsic cooperative active sites, facilitating the coupling of C and N species and achieving efficient urea synthesis. By density-functional theory (DFT) calculations, we verify that positively charged Mo atoms on the GBs exhibit high adsorption and reduction activity for CO<sub>2</sub>, whereas adjacent Mo atoms contribute to the activation of N<sub>2</sub> or NO. The cooperative effects of these active sites enables C-N coupling to proceed spontaneously on the GBs with ultralow limiting potentials (−0.24 ∼ −0.42 V). Furthermore, analysis of the competing hydrogen evolution reaction and nitrogen reduction reaction confirms the high selectivity to generate urea on Mo<sub>2</sub>C GBs. Our work demonstrates GB engineering as a promising strategy for urea generation through the synergistic cooperation between multiple active sites, thus paving the way towards the rational design of effective catalysts for urea electrosynthesis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116139"},"PeriodicalIF":6.5,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-11DOI: 10.1016/j.jcat.2025.116130
Valérie Toussaint, Stephanie Bachmann, Ann-Christin Pöppler, Vitaly L. Sushkevich, Gernot Friedbacher, Thomas Konegger, Lukas Brunnbauer, Andreas Limbeck, Christian Hametner, Günther Rupprechter, Irina Delidovich
Porous tin-organic frameworks (Sn-OFs) are composed of Lewis acid Sn4+ sites connected via organic linkers by tin-carbon covalent bonds. Although high activity of Sn-OFs for selective epimerization of D-glucose into D-mannose has been reported, the roles of different active sites of the Sn-OFs in catalysis remain under debate. Herein, four Sn-OFs with different aromatic linkers were synthesized and characterized using elemental analysis, low-temperature N2 adsorption, and SEM, along with ATR-IR, 1H, 13C, and 119Sn MAS NMR, XANES, and EXAFS spectroscopies. Comparative studies with organotin model molecules revealed tetraaryltin Ar4Sn as major structural element of the Sn-OFs with additional sites including dimers Ar3SnOSnAr3, alkylaryltin sites nBuxAr(4-x)Sn, and SnO2. Catalytic tests of the respective organotin molecules suggest Ar4Sn and Ar3SnOSnAr3 as active sites for the epimerization, whereas the activity of the latter bimolecular sites appears to be superior. In contrast, nBuxAr(4-x)Sn alkylaryltin sites and SnO2 contributed to the formation of side products, converting D-glucose into D-fructose. The Sn-OFs with symmetrical linkers are more structured materials exhibiting higher catalytic activity than the Sn-OFs with asymmetrical linkers. These findings clarify the roles of various Sn sites in Sn-OFs, advancing understanding of their catalytic behavior.
{"title":"Binuclear and mononuclear active sites of porous tin-organic frameworks for selective epimerization of D-glucose into D-mannose","authors":"Valérie Toussaint, Stephanie Bachmann, Ann-Christin Pöppler, Vitaly L. Sushkevich, Gernot Friedbacher, Thomas Konegger, Lukas Brunnbauer, Andreas Limbeck, Christian Hametner, Günther Rupprechter, Irina Delidovich","doi":"10.1016/j.jcat.2025.116130","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116130","url":null,"abstract":"Porous tin-organic frameworks (Sn-OFs) are composed of Lewis acid Sn<sup>4+</sup> sites connected <em>via</em> organic linkers by tin-carbon covalent bonds. Although high activity of Sn-OFs for selective epimerization of D-glucose into D-mannose has been reported, the roles of different active sites of the Sn-OFs in catalysis remain under debate. Herein, four Sn-OFs with different aromatic linkers were synthesized and characterized using elemental analysis, low-temperature N<sub>2</sub> adsorption, and SEM, along with ATR-IR, <sup>1</sup>H, <sup>13</sup>C, and <sup>119</sup>Sn MAS NMR, XANES, and EXAFS spectroscopies. Comparative studies with organotin model molecules revealed tetraaryltin Ar<sub>4</sub>Sn as major structural element of the Sn-OFs with additional sites including dimers Ar<sub>3</sub>Sn<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>O<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>SnAr<sub>3</sub>, alkylaryltin sites <sup>n</sup>Bu<sub>x</sub>Ar<sub>(4-x)</sub>Sn, and SnO<sub>2</sub>. Catalytic tests of the respective organotin molecules suggest Ar<sub>4</sub>Sn and Ar<sub>3</sub>Sn<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>O<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>SnAr<sub>3</sub> as active sites for the epimerization, whereas the activity of the latter bimolecular sites appears to be superior. In contrast, <sup>n</sup>Bu<sub>x</sub>Ar<sub>(4-x)</sub>Sn alkylaryltin sites and SnO<sub>2</sub> contributed to the formation of side products, converting D-glucose into D-fructose. The Sn-OFs with symmetrical linkers are more structured materials exhibiting higher catalytic activity than the Sn-OFs with asymmetrical linkers. These findings clarify the roles of various Sn sites in Sn-OFs, advancing understanding of their catalytic behavior.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"21 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Efficient carrier separation and catalytic microenvironment optimization are critical challenges in enhancing the coupling of photocatalytic CO2 reduction reaction (CO2RR) with H2O oxidation. Here, Ag-interstitial-doped TiO2 (Agi-TiO2) nanosheets were synthesized via stepwise solvothermal method and hybridized with CsPbBr3 ultrafine nanocubes to construct 0D/2D S-scheme CsPbBr3/Agi-TiO2 heterojunction. In-situ irradiated XPS (ISI-XPS) and femtosecond transient absorption spectroscopy (fs-TAS) verified that an Agi-mediated intermediate level (Agi-IL) initiated an additional interfacial charge transport pathway from Agi-IL to valence band (VB) of CsPbBr3. The CsPbBr3/Agi-TiO2 system exhibits dual-S-scheme characteristics, significantly enhancing the photogenerated charge separation. Furthermore, in-situ diffuse infrared Fourier transform spectroscopy (DRIFTS) combined with theoretical calculations revealed that the replacing long-chain oleylamine (OAm) ligands with short-chain octylamine (OTAm) on CsPbBr3 strengthens the binding affinity for *CO2 and *CO/*CHO intermediates, thereby modulating the product selectivity (CO vs. CH4). The CsPbBr3/Agi-TiO2 (CO: 143.7 µmol g−1h−1; electron selectivity: 91.7 %) and e-CsPbBr3/Agi-TiO2 (CH4: 57.2 µmol g−1h−1; electron selectivity: 78.0 %) showed good photocatalytic CO2RR activity and selectivity in the gas phase with H2O vapor as the proton source, without any sacrificial agents and cocatalysts. This study provides insights into the rational design of dual-S-scheme heterojunctions and the modulation of the reaction microenvironment in mixed-dimensional heterojunctions.
{"title":"Dual-S-scheme 0D/2D heterojunction of CsPbBr3/Agi-TiO2 for improved photocatalytic CO2 reduction: Enabling ultrafast interfacial charge transfer and product selective regulation","authors":"Zexiang Wang, Feng Xiang, Chen Chen, Jing Wang, Xiangchen Ma, Xian Zhao, Weiliu Fan","doi":"10.1016/j.jcat.2025.116112","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116112","url":null,"abstract":"Efficient carrier separation and catalytic microenvironment optimization are critical challenges in enhancing the coupling of photocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) with H<sub>2</sub>O oxidation. Here, Ag-interstitial-doped TiO<sub>2</sub> (Ag<sub>i</sub>-TiO<sub>2</sub>) nanosheets were synthesized via stepwise solvothermal method and hybridized with CsPbBr<sub>3</sub> ultrafine nanocubes to construct 0D/2D S-scheme CsPbBr<sub>3</sub>/Ag<sub>i</sub>-TiO<sub>2</sub> heterojunction. In-situ irradiated XPS (ISI-XPS) and femtosecond transient absorption spectroscopy (fs-TAS) verified that an Ag<sub>i</sub>-mediated intermediate level (Ag<sub>i</sub>-IL) initiated an additional interfacial charge transport pathway from Ag<sub>i</sub>-IL to valence band (VB) of CsPbBr<sub>3</sub>. The CsPbBr<sub>3</sub>/Ag<sub>i</sub>-TiO<sub>2</sub> system exhibits dual-S-scheme characteristics, significantly enhancing the photogenerated charge separation. Furthermore, in-situ diffuse infrared Fourier transform spectroscopy (DRIFTS) combined with theoretical calculations revealed that the replacing long-chain oleylamine (OAm) ligands with short-chain octylamine (OTAm) on CsPbBr<sub>3</sub> strengthens the binding affinity for *CO<sub>2</sub> and *CO/*CHO intermediates, thereby modulating the product selectivity (CO vs. CH<sub>4</sub>). The CsPbBr<sub>3</sub>/Ag<sub>i</sub>-TiO<sub>2</sub> (CO: 143.7 µmol g<sup>−1</sup>h<sup>−1</sup>; electron selectivity: 91.7 %) and e-CsPbBr<sub>3</sub>/Ag<sub>i</sub>-TiO<sub>2</sub> (CH<sub>4</sub>: 57.2 µmol g<sup>−1</sup>h<sup>−1</sup>; electron selectivity: 78.0 %) showed good photocatalytic CO<sub>2</sub>RR activity and selectivity in the gas phase with H<sub>2</sub>O vapor as the proton source, without any sacrificial agents and cocatalysts. This study provides insights into the rational design of dual-S-scheme heterojunctions and the modulation of the reaction microenvironment in mixed-dimensional heterojunctions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"117 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-11DOI: 10.1016/j.jcat.2025.116133
Kaikai Qiao , Haoran Li , Zhi Chen , Yong Zhu , Wenfeng Jiang , Fei Li , Lei Shi
Here we present a study on the generation of silanols from hydrosilanes in a photoelectrochemical cell consisting of a mesoporous BiVO4 photoanode and a platinum electrode using N-hydroxysuccinimide (NHS) as a HAT catalyst. The scheme prepared a variety of valuable silanols in high selectivity and moderate to good yields at room temperature. Notably, this photoelectrochemical approach equally applies to the functionalization of complex molecules. In addition, BiVO4 photoanodes show excellent stability in hydrolyzed hydrogen silanes.
{"title":"Photoelectrochemical oxidation of organosilanes to silanols with high selectivity","authors":"Kaikai Qiao , Haoran Li , Zhi Chen , Yong Zhu , Wenfeng Jiang , Fei Li , Lei Shi","doi":"10.1016/j.jcat.2025.116133","DOIUrl":"10.1016/j.jcat.2025.116133","url":null,"abstract":"<div><div>Here we present a study on the generation of silanols from hydrosilanes in a photoelectrochemical cell consisting of a mesoporous BiVO<sub>4</sub> photoanode and a platinum electrode using <em>N</em>-hydroxysuccinimide (NHS) as a HAT catalyst. The scheme prepared a variety of valuable silanols in high selectivity and moderate to good yields at room temperature. Notably, this photoelectrochemical approach equally applies to the functionalization of complex molecules. In addition, BiVO<sub>4</sub> photoanodes show excellent stability in hydrolyzed hydrogen silanes.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116133"},"PeriodicalIF":6.5,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-11DOI: 10.1016/j.jcat.2025.116140
Junyuan Xu, Xinyu Han, Lihua Zhu, Weizhen Wang, Luna Ruan, Zhiqing Yang, Hengqiang Ye, Bing Hui Chen
In this work, zeolitic imidazolate framework-67 (ZIF-67) is prepared by the hydrothermal method, and then carbon doping with nitrogen (NC)-supported cobalt is gained by the thermal treatment in N2 at 900 °C. The CuCo/NC bimetallic catalysts with different Cu and Co loadings (various Cu/Co mass ratios) are obtained by the galvanic replacement method. A series of characterization results (such as aberration-corrected scanning transmission electron microscopy (AC-STEM) and in-situ XPS) could prove that the nanostructure of the as-synthesized CuCo/NC bimetallic catalysts is that Cu-related species in the form of co-existence of single atoms and clusters is supported on the Co nanoparticles then on NC, and there is a synergy effect among Cu-, Co–, and N-related species. The CuCo/NC-2 (Cu-9.6 wt%, Co-29.7 wt%) catalyst prepared without noble metals demonstrated remarkable catalytic activity under mild reaction conditions (3.0 MPa H2, 100 °C, 6 h), achieving 51.3 % furfural (FF) conversion and 97.6 % furfuryl alcohol (FA) selectivity. In addition, density functional theory calculations further prove that Cu and Co form an electronic synergistic effect (electrons transferring from Co to Cu). On one hand, the introduction of Cu could significantly reduce the energy required for hydrogen dissociation. The energy required for hydrogen dissociation on CuCo/NC-2 is only 0.003 eV, much lower than the 0.382 eV required for Co/NC, so the active hydrogen species much more easily participate in the hydrogenation reaction. On the other hand, CuCo/NC has lower activation energy for the FF hydrogenation reaction, making the reaction easier to proceed. The activation energies required for the two-step reaction of adding H to the carbonyl group over CuCo/NC are only 1.657 eV and 1.245 eV, while Co/NC requires 2.410 eV and 2.405 eV, respectively. These two aspects play a crucial role in enhancing the catalytic performance (activity and selectivity to FA) of CuCo/NC for FF hydrogenation.
{"title":"Revealing the intrinsic relationship between nano/electronic structure of CuCo/NC (NC drived from ZIF-67) and their catalytic performance for furfural selective hydrogenation","authors":"Junyuan Xu, Xinyu Han, Lihua Zhu, Weizhen Wang, Luna Ruan, Zhiqing Yang, Hengqiang Ye, Bing Hui Chen","doi":"10.1016/j.jcat.2025.116140","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116140","url":null,"abstract":"In this work, zeolitic imidazolate framework-67 (ZIF-67) is prepared by the hydrothermal method, and then carbon doping with nitrogen (NC)-supported cobalt is gained by the thermal treatment in N<sub>2</sub> at 900 °C. The CuCo/NC bimetallic catalysts with different Cu and Co loadings (various Cu/Co mass ratios) are obtained by the galvanic replacement method. A series of characterization results (such as aberration-corrected scanning transmission electron microscopy (AC-STEM) and <em>in-situ</em> XPS) could prove that the nanostructure of the as-synthesized CuCo/NC bimetallic catalysts is that Cu-related species in the form of co-existence of single atoms and clusters is supported on the Co nanoparticles then on NC, and there is a synergy effect among Cu-, Co–, and N-related species. The CuCo/NC-2 (Cu-9.6 wt%, Co-29.7 wt%) catalyst prepared without noble metals demonstrated remarkable catalytic activity under mild reaction conditions (3.0 MPa H<sub>2</sub>, 100 °C, 6 h), achieving 51.3 % furfural (FF) conversion and 97.6 % furfuryl alcohol (FA) selectivity. In addition, density functional theory calculations further prove that Cu and Co form an electronic synergistic effect (electrons transferring from Co to Cu). On one hand, the introduction of Cu could significantly reduce the energy required for hydrogen dissociation. The energy required for hydrogen dissociation on CuCo/NC-2 is only 0.003 eV, much lower than the 0.382 eV required for Co/NC, so the active hydrogen species much more easily participate in the hydrogenation reaction. On the other hand, CuCo/NC has lower activation energy for the FF hydrogenation reaction, making the reaction easier to proceed. The activation energies required for the two-step reaction of adding H to the carbonyl group over CuCo/NC are only 1.657 eV and 1.245 eV, while Co/NC requires 2.410 eV and 2.405 eV, respectively. These two aspects play a crucial role in enhancing the catalytic performance (activity and selectivity to FA) of CuCo/NC for FF hydrogenation.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"15 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822929","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-10DOI: 10.1016/j.jcat.2025.116135
Jing Zhang , Yan Liu , Chao Yang , Yanyan Qu , Aodi Zhang , Zhenzhen Feng , Wentao Wang , Pengfei Ou
Designing efficient and stable bifunctional oxygen evolution/reduction reaction (OER/ORR) electrocatalysts is important to developing renewable energy technologies. However, integrating OER/ORR activity in a single electrocatalyst remains challenging due to the difficulty in balancing the adsorption strengths of reaction intermediates. Herein, density functional theory (DFT) calculations were conducted to investigate 4d-transition metal (TM) doped graphitic carbon nitride (4d-TM@C3N3) systems as potential bifunctional OER/ORR electrocatalysts by considering the charge states through a defect physics method. Our results identified 30 stable 4d-TMN@C3N3 systems, including TM doped at nitrogen sites (4d-TMN@C3N3) and those occupying interstitial sites (4d-TMint@C3N3). Machine learning analysis showed that the the bond lengths between TM and O (dTM-O) and OH (dTM-OH), and the charge transfer of TM atoms (Qe) are the three primary descriptors characterizing the adsorption behavior. Among these, Pdint×@C3N3 (Pd interstitial site, neutral charge state), Pdint•@C3N3 (Pd interstitial site, +1 charge state), and Rhint•@C3N3 (Rh interstitial site, +1 charge state) exhibit outstanding OER/ORR catalytic activity with ηOER/ηORR of 0.56/0.37 V, 0.66/0.37 V, and 0.59/0.44 V, respectively, which are comparable to benchmark electrocatalysts such as RuO2 for OER (0.69 V) and Pt for ORR (0.61 V). The enhanced performance arises from charged defects adjustment that optimizes the bifunctional OER/ORR activity, offering potential electrocatalysts for energy conversion applications.
{"title":"Design of bifunctional oxygen evolution/reduction electrocatalysts on g-C3N3 monolayer by a defect physics method","authors":"Jing Zhang , Yan Liu , Chao Yang , Yanyan Qu , Aodi Zhang , Zhenzhen Feng , Wentao Wang , Pengfei Ou","doi":"10.1016/j.jcat.2025.116135","DOIUrl":"10.1016/j.jcat.2025.116135","url":null,"abstract":"<div><div>Designing efficient and stable bifunctional oxygen evolution/reduction reaction (OER/ORR) electrocatalysts is important to developing renewable energy technologies. However, integrating OER/ORR activity in a single electrocatalyst remains challenging due to the difficulty in balancing the adsorption strengths of reaction intermediates. Herein, density functional theory (DFT) calculations were conducted to investigate 4d-transition metal (TM) doped graphitic carbon nitride (4d-TM@C<sub>3</sub>N<sub>3</sub>) systems as potential bifunctional OER/ORR electrocatalysts by considering the charge states through a defect physics method. Our results identified 30 stable 4d-TM<sub>N</sub>@C<sub>3</sub>N<sub>3</sub> systems, including TM doped at nitrogen sites (4d-TM<sub>N</sub>@C<sub>3</sub>N<sub>3</sub>) and those occupying interstitial sites (4d-TM<sub>int</sub>@C<sub>3</sub>N<sub>3</sub>). Machine learning analysis showed that the the bond lengths between TM and O (<em>d</em><sub>TM-O</sub>) and OH (<em>d</em><sub>TM-OH</sub>), and the charge transfer of TM atoms (<em>Q</em><sub>e</sub>) are the three primary descriptors characterizing the adsorption behavior. Among these, Pd<sub>int</sub><sup>×</sup>@C<sub>3</sub>N<sub>3</sub> (Pd interstitial site, neutral charge state), Pd<sub>int</sub><sup>•</sup>@C<sub>3</sub>N<sub>3</sub> (Pd interstitial site, +1 charge state), and Rh<sub>int</sub><sup>•</sup>@C<sub>3</sub>N<sub>3</sub> (Rh interstitial site, +1 charge state) exhibit outstanding OER/ORR catalytic activity with <em>η</em><sup>OER</sup>/<em>η</em><sup>ORR</sup> of 0.56/0.37 V, 0.66/0.37 V, and 0.59/0.44 V, respectively, which are comparable to benchmark electrocatalysts such as RuO<sub>2</sub> for OER (0.69 V) and Pt for ORR (0.61 V). The enhanced performance arises from charged defects adjustment that optimizes the bifunctional OER/ORR activity, offering potential electrocatalysts for energy conversion applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116135"},"PeriodicalIF":6.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-10DOI: 10.1016/j.jcat.2025.116136
Rasika Jayarathna, Rahat Javaid, Jochen Lauterbach
The role of metal oxide supports is complex in heterogeneous catalysis due to acidity, basicity, and surface defects. Interpretable machine learning models trained on experimental data could lead to new insights about these complexities, which are rarely verified through detailed catalyst characterization. This study explores the role of metal oxide supports for the Ru-based ammonia synthesis catalysts using Shapley additive explanations (SHAP). The support metal nitride formation energy and the support metal hydride formation energy were identified as critical descriptors that could describe the ammonia synthesis activity. These descriptors and the related catalyst characterization by Ammonia-Temperature Programmed Desorption and Hydrogen-Temperature Programmed Desorption suggest new processes that could govern the ammonia synthesis reaction. It is suggested that in addition to basicity, the metal oxide support should possess a certain acidity to alleviate ammonia inhibition and form metal hydrides to alleviate hydrogen inhibition.
{"title":"Understanding the role of metal oxide support in ruthenium-based catalysts for ammonia synthesis via interpretable machine learning","authors":"Rasika Jayarathna, Rahat Javaid, Jochen Lauterbach","doi":"10.1016/j.jcat.2025.116136","DOIUrl":"10.1016/j.jcat.2025.116136","url":null,"abstract":"<div><div>The role of metal oxide supports is complex in heterogeneous catalysis due to acidity, basicity, and surface defects. Interpretable machine learning models trained on experimental data could lead to new insights about these complexities, which are rarely verified through detailed catalyst characterization. This study explores the role of metal oxide supports for the Ru-based ammonia synthesis catalysts using Shapley additive explanations (SHAP). The support metal nitride formation energy and the support metal hydride formation energy were identified as critical descriptors that could describe the ammonia synthesis activity. These descriptors and the related catalyst characterization by Ammonia-Temperature Programmed Desorption and Hydrogen-Temperature Programmed Desorption suggest new processes that could govern the ammonia synthesis reaction. It is suggested that in addition to basicity, the metal oxide support should possess a certain acidity to alleviate ammonia inhibition and form metal hydrides to alleviate hydrogen inhibition.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116136"},"PeriodicalIF":6.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-08DOI: 10.1016/j.jcat.2025.116137
Chenglei Xiao , Jinpeng Liang , Xianzi Wang , Yayun Pang , Kongqian Liang , Zhaoxi Cai , Zhimin Xue , Yanfei Zhao , Baowen Zhou , Jinliang Song
Hydrogenolytic cleavage of aromatic C-O ether bond in lignin derivatives provides a promising protocol for sustainable lignin upgrading. However, it remains a great challenge to make this attractive strategy occur under ambient temperature. Herein, we reported a solvent and electric cooperative catalytic system for hydrogenolytic cleavage of 4-O-5 lignin models. This proposed catalytic system was constructed by calcium titanate (CaTiO3)-supported Ru nanoparticles (Ru/CaTiO3) as the catalyst and isopropanol as the reaction solvent. Very interestingly, the 4-O-5 lignin models could be cleaved by hydrogenolysis at ambient temperature in this constructed catalytic system. Detailed investigations revealed that the hydrogenolysis occurred by the transfer of hydrogens in isopropanol, while the involved H2 played the role on hydrogenation of the in situ generated acetone, making the Ru0 sites available for successive hydrogenolysis. The high activity of this catalytic system (Ru/CaTiO3 with isopropanol) at ambient conditions originated from the synergistic effect of the more negatively charged metallic Ru0 sites (electronic effect) and the isopropanol acting as both the solvent and hydrogen donor (solvent effect).
{"title":"Ambient-temperature hydrogenolysis of 4-O-5 lignin model compounds to generate cyclohexanes and cyclohexanols enabled by synergy of electronic and solvent effects","authors":"Chenglei Xiao , Jinpeng Liang , Xianzi Wang , Yayun Pang , Kongqian Liang , Zhaoxi Cai , Zhimin Xue , Yanfei Zhao , Baowen Zhou , Jinliang Song","doi":"10.1016/j.jcat.2025.116137","DOIUrl":"10.1016/j.jcat.2025.116137","url":null,"abstract":"<div><div>Hydrogenolytic cleavage of aromatic C-O ether bond in lignin derivatives provides a promising protocol for sustainable lignin upgrading. However, it remains a great challenge to make this attractive strategy occur under ambient temperature. Herein, we reported a solvent and electric cooperative catalytic system for hydrogenolytic cleavage of 4-O-5 lignin models. This proposed catalytic system was constructed by calcium titanate (CaTiO<sub>3</sub>)-supported Ru nanoparticles (Ru/CaTiO<sub>3</sub>) as the catalyst and isopropanol as the reaction solvent. Very interestingly, the 4-O-5 lignin models could be cleaved by hydrogenolysis at ambient temperature in this constructed catalytic system. Detailed investigations revealed that the hydrogenolysis occurred by the transfer of hydrogens in isopropanol, while the involved H<sub>2</sub> played the role on hydrogenation of the in situ generated acetone, making the Ru<sup>0</sup> sites available for successive hydrogenolysis. The high activity of this catalytic system (Ru/CaTiO<sub>3</sub> with isopropanol) at ambient conditions originated from the synergistic effect of the more negatively charged metallic Ru<sup>0</sup> sites (electronic effect) and the isopropanol acting as both the solvent and hydrogen donor (solvent effect).</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116137"},"PeriodicalIF":6.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806573","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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