Pub Date : 2025-04-19DOI: 10.1016/j.jcat.2025.116146
Seongjun Lee, Jungwon Yun, Dasol Bae, Dohyeon Kim, Sung Bong Kang, Dohyung Kang, Minkyu Kim
The selective conversion of small alkanes into value-added products presents a significant challenge in catalysis due to the strong tendency toward complete oxidation. In this study, we employed DFT calculations and TPRS simulations to investigate ethane oxidation on the RhO2(1 1 0) surface. Our results demonstrate that the moderate reactivity of RhO2(1 1 0) enhances selectivity for ethylene production, positioning RhO2(1 1 0) as a promising catalyst for the selective oxidation of small alkanes and improved yields of value-added products. Extending beyond RhO2, we propose that highly reactive transition metal oxide surfaces may exhibit similar C2H4 desorption mechanisms involving C2H4 reformation-based desorption, as supported by comparisons with highly active IrO2. This insight suggests that catalytic strategies designed to facilitate reverse reactions for C2H4 reformation hold potential for boosting C2H4(g) production from C2H6 oxidation on active transition metal oxides.
{"title":"Selective conversion of ethane to value added products on RhO2(1 1 0): A DFT and microkinetic simulation study","authors":"Seongjun Lee, Jungwon Yun, Dasol Bae, Dohyeon Kim, Sung Bong Kang, Dohyung Kang, Minkyu Kim","doi":"10.1016/j.jcat.2025.116146","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116146","url":null,"abstract":"The selective conversion of small alkanes into value-added products presents a significant challenge in catalysis due to the strong tendency toward complete oxidation. In this study, we employed DFT calculations and TPRS simulations to investigate ethane oxidation on the RhO<sub>2</sub>(1<!-- --> <!-- -->1<!-- --> <!-- -->0) surface. Our results demonstrate that the moderate reactivity of RhO<sub>2</sub>(1<!-- --> <!-- -->1<!-- --> <!-- -->0) enhances selectivity for ethylene production, positioning RhO<sub>2</sub>(1<!-- --> <!-- -->1<!-- --> <!-- -->0) as a promising catalyst for the selective oxidation of small alkanes and improved yields of value-added products. Extending beyond RhO<sub>2</sub>, we propose that highly reactive transition metal oxide surfaces may exhibit similar C<sub>2</sub>H<sub>4</sub> desorption mechanisms involving C<sub>2</sub>H<sub>4</sub> reformation-based desorption, as supported by comparisons with highly active IrO<sub>2</sub>. This insight suggests that catalytic strategies designed to facilitate reverse reactions for C<sub>2</sub>H<sub>4</sub> reformation hold potential for boosting C<sub>2</sub>H<sub>4</sub>(g) production from C<sub>2</sub>H<sub>6</sub> oxidation on active transition metal oxides.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"28 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853867","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}
Heterogeneously catalytic depolymerization of lignin into value-added biochemicals are imperative, yet challengeable by the limited mass transport of lignin and the non-ideal spatial distributions of active sites in catalysts. Herein, a series of polycrystalline materials with Cu and Fe oxides encapsulated in hierarchical hollow nano silicalite (Cux-Fey@HhNS) were designed for step-by-step oxidative conversion of lignin into diethyl meleate (DEM). 92.0 % conversion of lignin with an exceptional DEM yield of 31.2 wt% and selectivity of 70.7 % was achieved at 150 °C for 24 h using Cu2.5-Fe2.2@HhNS. A series of controlled experiments and characterization showed clearly that the superior performance in DEM production was attributed to the enhanced tandem processes of lignin Cα-Cβ bonds deconstruction by framework Cu2+, subsequently aromatic ring-cleavage by the isolated framework Fe3+, and the well-balanced micro-/mesoporosity ratio of Cux-Fey@HhNS facilitates the diffusion of lignin macromolecules/products, contributing to the excellent DEM yield and selectivity as well. Further mechanistic investigation illustrated that the process proceeds via a single electron transfer pathway. Consequently, this work provides new insights into lignin valorization to bulk chemicals, paving the way for biomass-derived recyclable polymeric materials as sustainable alternative to traditional petroleum-based routes.
{"title":"Hierarchical hollow silicalite encapsulated Cu-Fe oxides for selectively oxidative depolymerization of lignin to diethyl meleate","authors":"Lixia Li, Juanhua Kong, Jinxing Long, Zhengping Cai, Qiang Zeng, Kejia Wu, Yingying Zhan, Sijie Liu, Hongyan He, Xuehui Li","doi":"10.1016/j.jcat.2025.116157","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116157","url":null,"abstract":"Heterogeneously catalytic depolymerization of lignin into value-added biochemicals are imperative, yet challengeable by the limited mass transport of lignin and the non-ideal spatial distributions of active sites in catalysts. Herein, a series of polycrystalline materials with Cu and Fe oxides encapsulated in hierarchical hollow nano silicalite (Cu<em><sub>x</sub></em>-Fe<em><sub>y</sub></em>@HhNS) were designed for step-by-step oxidative conversion of lignin into diethyl meleate (DEM). 92.0 % conversion of lignin with an exceptional DEM yield of 31.2 wt% and selectivity of 70.7 % was achieved at 150 °C for 24 h using Cu<sub>2.5</sub>-Fe<sub>2.2</sub>@HhNS. A series of controlled experiments and characterization showed clearly that the superior performance in DEM production was attributed to the enhanced tandem processes of lignin C<em><sub>α</sub></em>-C<em><sub>β</sub></em> bonds deconstruction by framework Cu<sup>2+</sup>, subsequently aromatic ring-cleavage by the isolated framework Fe<sup>3+</sup>, and the well-balanced micro-/mesoporosity ratio of Cu<em><sub>x</sub></em>-Fe<em><sub>y</sub></em>@HhNS facilitates the diffusion of lignin macromolecules/products, contributing to the excellent DEM yield and selectivity as well. Further mechanistic investigation illustrated that the process proceeds <em>via</em> a single electron transfer pathway. Consequently, this work provides new insights into lignin valorization to bulk chemicals, paving the way for biomass-derived recyclable polymeric materials as sustainable alternative to traditional petroleum-based routes.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"10 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849888","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 : 2025-04-18DOI: 10.1016/j.jcat.2025.116155
Kang Gao , Guangjing Feng , Chaoan Liang , Zhuang Wang , Xiaoyan Sun , Jianhua Liu , Chungu Xia , Yuxiao Ding
Trans-2-butene is regularly burned as a liquefied petroleum gas (LPG) component in several developing countries due to its inertness and inseparability in comparison to other butene isomers (1-butene and isobutene), resulting in low-value utilization of resource and environmental degradation. The generation of high-carbon olefins via trans-2-butene oligomerization has become one of the most effective ways for its high-value valorization. Octene is currently undersupplied via ethylene oligomerization, and its traditional crafts are costly due to separation from full-fraction α-olefins (C4-C30). In the present work, we synthesized a series of novel 2-phenyl-ketimine-1,10-phenanthroline iron complexes (Fe0-Fe9). Fe2 catalyst realizes the dimerization of trans-2-butene through homogeneous catalysis at moderate conditions (0.2 MPa, 30 °C), obtaining 3,4-dimethyl-1-hexene with 99.9 % selectivity. In contrast to the reported heterogeneous catalysts, our catalytic system exhibits a considerable improvement in activity and selectivity.
{"title":"Unparalleled dimerization of trans-2-butene to 3,4-dimethyl-1-hexene on iron-based catalyst","authors":"Kang Gao , Guangjing Feng , Chaoan Liang , Zhuang Wang , Xiaoyan Sun , Jianhua Liu , Chungu Xia , Yuxiao Ding","doi":"10.1016/j.jcat.2025.116155","DOIUrl":"10.1016/j.jcat.2025.116155","url":null,"abstract":"<div><div><em>Trans</em>-2-butene is regularly burned as a liquefied petroleum gas (LPG) component in several developing countries due to its inertness and inseparability in comparison to other butene isomers (1-butene and isobutene), resulting in low-value utilization of resource and environmental degradation. The generation of high-carbon olefins via <em>trans</em>-2-butene oligomerization has become one of the most effective ways for its high-value valorization. Octene is currently undersupplied via ethylene oligomerization, and its traditional crafts are costly due to separation from full-fraction α-olefins (C<sub>4</sub>-C<sub>30</sub>). In the present work, we synthesized a series of novel 2-phenyl-ketimine-1,10-phenanthroline iron complexes (Fe0-Fe9). Fe2 catalyst realizes the dimerization of <em>trans</em>-2-butene through homogeneous catalysis at moderate conditions (0.2 MPa, 30 °C), obtaining 3,4-dimethyl-1-hexene with 99.9 % selectivity. In contrast to the reported heterogeneous catalysts, our catalytic system exhibits a considerable improvement in activity and selectivity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116155"},"PeriodicalIF":6.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849887","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 : 2025-04-18DOI: 10.1016/j.jcat.2025.116154
Heng Yang, Yan Jiao, Guodong Zhang, Pan Gao, Feng Chen
Esters are fundamental compounds in materials science, medicinal chemistry, and organic synthesis. Numerous synthetic methods have been developed to construct ester functional groups. The transition metal-catalyzed carbonylation of aryl halides with alcohols is well-established, with palladium catalysts being the most commonly used. However, the development of non-noble metal-based catalysts for carbonylation reactions has become attractive due to their cost-effectiveness. In this study, we report a novel homogeneous cobalt-catalyzed system for the carbonylation of aryl bromides and aryl chlorides with alkyl halides directly. Notably, this methodology efficiently prepares specialized esters using inexpensive alkyl halides, offering a more economical alternative to using the corresponding alcohols.
{"title":"Cobalt-catalyzed esterification of organohalides with carbon monoxide","authors":"Heng Yang, Yan Jiao, Guodong Zhang, Pan Gao, Feng Chen","doi":"10.1016/j.jcat.2025.116154","DOIUrl":"10.1016/j.jcat.2025.116154","url":null,"abstract":"<div><div>Esters are fundamental compounds in materials science, medicinal chemistry, and organic synthesis. Numerous synthetic methods have been developed to construct ester functional groups. The transition metal-catalyzed carbonylation of aryl halides with alcohols is well-established, with palladium catalysts being the most commonly used. However, the development of non-noble metal-based catalysts for carbonylation reactions has become attractive due to their cost-effectiveness. In this study, we report a novel homogeneous cobalt-catalyzed system for the carbonylation of aryl bromides and aryl chlorides with alkyl halides directly. Notably, this methodology efficiently prepares specialized esters using inexpensive alkyl halides, offering a more economical alternative to using the corresponding alcohols.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116154"},"PeriodicalIF":6.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849886","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 : 2025-04-17DOI: 10.1016/j.jcat.2025.116152
Chongqing Wang , Jianfei Dang , Yajing Han , Qinggan Zeng , Liqiang Wang
Developing noble metal-free catalysts that enable hydrogenation reduction of nitro compounds to perform under mild conditions is highly attractive yet remains a significant challenge. Herein, carbon nanotube-supported Co-N-C with abundant mesopores (Co1/CoNPs@CNT) was synthesized via in situ pyrolysis of zeolitic imidazolate framework-67 encapsulated ZnO (ZnO@ZIF-67) for catalytic hydrogenation. The Co1/CoNPs@CNT catalyst features abundant atomically dispersed CoNx active sites that are easily accessible to substrates. Additionally, theoretical calculations suggest CoNx on curved surfaces favours the H2 dissociation and the second NO bond breaking (PhNOH* + H* → PhN* + H2O) more than that on flat surfaces, two crucial steps in the hydrogenation of nitro compounds. As a result, Co1/CoNPs@CNT exhibits outstanding catalytic performance, enabling the hydrogenation reaction to go smoothly under mild conditions (50 °C, 1 bar H2) with high conversion and selectivity across a range of substrates.
{"title":"Carbon nanotube-supported Co-N-C with enriched mesopores for hydrogenation of nitro compounds","authors":"Chongqing Wang , Jianfei Dang , Yajing Han , Qinggan Zeng , Liqiang Wang","doi":"10.1016/j.jcat.2025.116152","DOIUrl":"10.1016/j.jcat.2025.116152","url":null,"abstract":"<div><div>Developing noble metal-free catalysts that enable hydrogenation reduction of nitro compounds to perform under mild conditions is highly attractive yet remains a significant challenge. Herein, carbon nanotube-supported Co-N-C with abundant mesopores (Co<sub>1</sub>/CoNPs@CNT) was synthesized via in situ pyrolysis of zeolitic imidazolate framework-67 encapsulated ZnO (ZnO@ZIF-67) for catalytic hydrogenation. The Co<sub>1</sub>/CoNPs@CNT catalyst features abundant atomically dispersed CoNx active sites that are easily accessible to substrates. Additionally, theoretical calculations suggest CoNx on curved surfaces favours the H<sub>2</sub> dissociation and the second N<img>O bond breaking (PhNOH* + H* → PhN* + H<sub>2</sub>O) more than that on flat surfaces, two crucial steps in the hydrogenation of nitro compounds. As a result, Co<sub>1</sub>/CoNPs@CNT exhibits outstanding catalytic performance, enabling the hydrogenation reaction to go smoothly under mild conditions (50 °C, 1 bar H<sub>2</sub>) with high conversion and selectivity across a range of substrates.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116152"},"PeriodicalIF":6.5,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847021","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 : 2025-04-16DOI: 10.1016/j.jcat.2025.116147
Hui Zhang , Jing Wang , Caiping Ma , Riguang Zhang , Baojun Wang , Yang Zhang , Xiaofeng Li , Lixia Ling
The HZSM-5 catalyst modified with Ga species exhibits excellent reaction performance for propane dehydroaromatization, a process that involves propane dehydrogenation to propylene, and further formation of aromatics via polymerization, cyclization, dehydrogenation, etc. The detailed mechanism of the synergistic effect between Ga species and Brønsted acid with each other during propane dehydroaromatization remains unclear due to the complexity and extreme branching of aromatization reaction pathways. In this study, the complete reaction process for propane dehydroaromatization on Ga-modified HZSM-5 is investigated based on the density functional theory (DFT) method. The results indicate that the Ga-modified HZSM-5 catalysts with [GaH]2+ species at all studied sites show superior thermodynamic and kinetic stability, with only [GaH]2+ species at the T3-T11 and T3-T5 sites exhibiting excellent dehydrogenation performance. In propane dehydroaromatization, the dehydrogenation reactions dominated by [GaH]2+ species tend to occur on the framework O atom surrounding [GaH]2+ species with stronger Lewis base strength, while polymerization and cyclization reactions dominated by Brønsted acid tend to occur on Brønsted acid with stronger acid strength. The synergistic effect between [GaH]2+ species and Brønsted acid is reflected in the fact that the [GaH]2+ species can indirectly improve the activity of propylene polymerization and C6 diene cyclization reactions on the Brønsted acid by enhancing the Brønsted acid strength, and in turn, the Brønsted acid enables the [GaH]2+ species to exist more stably kinetically by promoting the conversion of [GaH2]+ species to [GaH]2+ species. This study contributes to the enriched understanding of the Brønsted/Lewis acid synergistic effect and the role of acidity-basicity during propane dehydroaromatization on Ga-modified HZSM-5.
{"title":"Propane dehydroaromatization on Ga-modified HZSM-5 catalyst: Brønsted/Lewis acid synergistic effect","authors":"Hui Zhang , Jing Wang , Caiping Ma , Riguang Zhang , Baojun Wang , Yang Zhang , Xiaofeng Li , Lixia Ling","doi":"10.1016/j.jcat.2025.116147","DOIUrl":"10.1016/j.jcat.2025.116147","url":null,"abstract":"<div><div>The HZSM-5 catalyst modified with Ga species exhibits excellent reaction performance for propane dehydroaromatization, a process that involves propane dehydrogenation to propylene, and further formation of aromatics via polymerization, cyclization, dehydrogenation, etc. The detailed mechanism of the synergistic effect between Ga species and Brønsted acid with each other during propane dehydroaromatization remains unclear due to the complexity and extreme branching of aromatization reaction pathways. In this study, the complete reaction process for propane dehydroaromatization on Ga-modified HZSM-5 is investigated based on the density functional theory (DFT) method. The results indicate that the Ga-modified HZSM-5 catalysts with [GaH]<sup>2+</sup> species at all studied sites show superior thermodynamic and kinetic stability, with only [GaH]<sup>2+</sup> species at the T3-T11 and T3-T5 sites exhibiting excellent dehydrogenation performance. In propane dehydroaromatization, the dehydrogenation reactions dominated by [GaH]<sup>2+</sup> species tend to occur on the framework O atom surrounding [GaH]<sup>2+</sup> species with stronger Lewis base strength, while polymerization and cyclization reactions dominated by Brønsted acid tend to occur on Brønsted acid with stronger acid strength. The synergistic effect between [GaH]<sup>2+</sup> species and Brønsted acid is reflected in the fact that the [GaH]<sup>2+</sup> species can indirectly improve the activity of propylene polymerization and C6 diene cyclization reactions on the Brønsted acid by enhancing the Brønsted acid strength, and in turn, the Brønsted acid enables the [GaH]<sup>2+</sup> species to exist more stably kinetically by promoting the conversion of [GaH<sub>2</sub>]<sup>+</sup> species to [GaH]<sup>2+</sup> species. This study contributes to the enriched understanding of the Brønsted/Lewis acid synergistic effect and the role of acidity-basicity during propane dehydroaromatization on Ga-modified HZSM-5.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116147"},"PeriodicalIF":6.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842124","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 : 2025-04-16DOI: 10.1016/j.jcat.2025.116151
J. Redondo , J. Subbian , M.A. Monclús , A. Pendashteh , D. Pérez , M. Mehdi , J. Ruiz-Hervías , J.M. Molina Aldareguia , J. LLorca
Platinum-group metals are currently the most efficient catalysts for hydrogen evolution reaction (HER), however their high cost and scarcity urge introduction and development of affordable alternatives. Herein, the effect of elastic strains on gold (Au) thin films is investigated to tune and enhance their catalytic activity towards HER. Tensile and compressive strains are introduced into Au films deposited via magnetron sputtering onto nitinol substrates using one-way shape memory effect of the alloy. The generated elastic strains are measured by X-ray diffraction, revealing maximum ∼ 0.43 % tension and ∼ 0.25 % compression. Electrochemical tests demonstrate that applying tensile strains to the Au thin film increases the HER catalytic activity, e.g., by reducing the overpotential at 50 mA/cm2 by 24 %. On the contrary, compressive strains decrease the catalytic activity, resulting in an increased overpotential of 32 %. Such effect is further confirmed from the kinetics study through Tafel analysis and charge transfer resistance measurements. Accordingly, this study not only results in Au samples with improved HER activity but also paves the path towards better understanding and application of elastic strain engineering for metals with enhanced catalytic activity for sustainable hydrogen production.
{"title":"Effect of elastic strains on the electrocatalytic activity of Au thin films for the hydrogen evolution reaction","authors":"J. Redondo , J. Subbian , M.A. Monclús , A. Pendashteh , D. Pérez , M. Mehdi , J. Ruiz-Hervías , J.M. Molina Aldareguia , J. LLorca","doi":"10.1016/j.jcat.2025.116151","DOIUrl":"10.1016/j.jcat.2025.116151","url":null,"abstract":"<div><div>Platinum-group metals are currently the most efficient catalysts for hydrogen evolution reaction (HER), however their high cost and scarcity urge introduction and development of affordable alternatives. Herein, the effect of elastic strains on gold (Au) thin films is investigated to tune and enhance their catalytic activity towards HER. Tensile and compressive strains are introduced into Au films deposited via magnetron sputtering onto nitinol substrates using one-way shape memory effect of the alloy. The generated elastic strains are measured by X-ray diffraction, revealing maximum ∼ 0.43 % tension and ∼ 0.25 % compression. Electrochemical tests demonstrate that applying tensile strains to the Au thin film increases the HER catalytic activity, e.g., by reducing the overpotential at 50 mA/cm<sup>2</sup> by 24 %. On the contrary, compressive strains decrease the catalytic activity, resulting in an increased overpotential of 32 %. Such effect is further confirmed from the kinetics study through Tafel analysis and charge transfer resistance measurements. Accordingly, this study not only results in Au samples with improved HER activity but also paves the path towards better understanding and application of elastic strain engineering for metals with enhanced catalytic activity for sustainable hydrogen production.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116151"},"PeriodicalIF":6.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842123","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 : 2025-04-16DOI: 10.1016/j.jcat.2025.116148
Henrik H. Kristoffersen
A huge issue in computational electrochemistry is that different modelling approaches, used to study electron transfer reactions, give different results that cannot easily be reconciled with each other. Modeling approaches differ in their handling of interface charging and employed electrolyte model. I study charging of electrolyte-Cu(111) interfaces with electrons and cations (or positive continuum charge) and observe that charging energies (i.e. the energy stabilization from charging the interface with one extra electron and thereby going from one potential to another) depend strongly on the electrolyte model. When the electrolyte is a film containing water molecules, there is a significant stabilization of the energy with more negative potential. This is in contrast to the charging of an interface with implicit solvent, where charge repulsion result in low stabilization of the energy with more negative potential. Therefore, modelling with implicit solvent gives the impression that changing has small effect on constant potential reaction energies and, consequently, that charging can be ignored. This is likely erroneous. I further consider constant potential CO2 adsorption to highlight the importance of charging and using an electrolyte model with water molecules, and show that other modelling approaches gives significantly different CO2 adsorption energies.
{"title":"Impact of charging in constant potential electrochemistry modelling","authors":"Henrik H. Kristoffersen","doi":"10.1016/j.jcat.2025.116148","DOIUrl":"10.1016/j.jcat.2025.116148","url":null,"abstract":"<div><div>A huge issue in computational electrochemistry is that different modelling approaches, used to study electron transfer reactions, give different results that cannot easily be reconciled with each other. Modeling approaches differ in their handling of interface charging and employed electrolyte model. I study charging of electrolyte-Cu(111) interfaces with electrons and cations (or positive continuum charge) and observe that charging energies (i.e. the energy stabilization from charging the interface with one extra electron and thereby going from one potential to another) depend strongly on the electrolyte model. When the electrolyte is a film containing water molecules, there is a significant stabilization of the energy with more negative potential. This is in contrast to the charging of an interface with implicit solvent, where charge repulsion result in low stabilization of the energy with more negative potential. Therefore, modelling with implicit solvent gives the impression that changing has small effect on constant potential reaction energies and, consequently, that charging can be ignored. This is likely erroneous. I further consider constant potential CO<sub>2</sub> adsorption to highlight the importance of charging and using an electrolyte model with water molecules, and show that other modelling approaches gives significantly different CO<sub>2</sub> adsorption energies.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116148"},"PeriodicalIF":6.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842121","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 : 2025-04-16DOI: 10.1016/j.jcat.2025.116145
Nicholas Marcella , Ryuichi Shimogawa , Yongchun Xiang , Anatoly I. Frenkel
Understanding the mechanisms of work of nanoparticle catalysts requires the knowledge of their structural and electronic descriptors, often measured in operando X-ray absorption fine structure (XAFS) spectroscopy experiments. We introduce a neural-network-based framework for rapidly mapping the extended XAFS (EXAFS) spectra onto structural parameters as an alternative to the commonly used non-linear least-squares fitting approaches. Our method leverages a multilayer perceptron trained on theoretical EXAFS and validated against theoretical test data and experimental spectra of frequently used nanoparticle types. The network helps lower the correlation between parameters, achieves high accuracy in the presence of noise and glitches, and can provide real-time parameter predictions with minimal user intervention. Parameter uncertainties are estimated as well. This method can be readily integrated into beamline pipelines or laboratory data analysis workflow and has the potential to accelerate high-throughput catalyst characterization and testing.
{"title":"First shell EXAFS data analysis of nanocatalysts via neural networks","authors":"Nicholas Marcella , Ryuichi Shimogawa , Yongchun Xiang , Anatoly I. Frenkel","doi":"10.1016/j.jcat.2025.116145","DOIUrl":"10.1016/j.jcat.2025.116145","url":null,"abstract":"<div><div>Understanding the mechanisms of work of nanoparticle catalysts requires the knowledge of their structural and electronic descriptors, often measured in operando X-ray absorption fine structure (XAFS) spectroscopy experiments. We introduce a neural-network-based framework for rapidly mapping the extended XAFS (EXAFS) spectra onto structural parameters as an alternative to the commonly used non-linear least-squares fitting approaches. Our method leverages a multilayer perceptron trained on theoretical EXAFS and validated against theoretical test data and experimental spectra of frequently used nanoparticle types. The network helps lower the correlation between parameters, achieves high accuracy in the presence of noise and glitches, and can provide real-time parameter predictions with minimal user intervention. Parameter uncertainties are estimated as well. This method can be readily integrated into beamline pipelines or laboratory data analysis workflow and has the potential to accelerate high-throughput catalyst characterization and testing.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116145"},"PeriodicalIF":6.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842122","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 : 2025-04-15DOI: 10.1016/j.jcat.2025.116141
Guangyu An , Bo Gao , Song Xu , Chaozheng Zhou , Wenzhuo Wu , Keying Li , Qun Xu
Transition metal doping is a well-established strategy to modulate the electronic structure of 2D transition metal dichalcogenide (TMD) for efficient electrocatalysis. Conventionally, the oxidation state of the heterometal doped in 2D TMD is divalent, which limited its electronic perturbation strength towards active sites. Therefore, introducing low-valent heterometal into 2D TMD is proposed to be a feasible strategy to enhance the electronic perturbation through the presence of additional d electrons, leading to novel electrocatalytic activity. As a proof of concept, Co(0) is introduced into MoS2 (Co(0)-MoS2) through “intercalation-vulcanization” in this work. Comparing to Co(II) doped MoS2 (Co(II)-MoS2), the presence of additional d electrons at Co dopant in Co(0)-MoS2 facilitated the electronic perturbation between “Co-S-Mo” atoms, which optimizes the electronic structure of the active sites at MoS2. As results, the H2O dissociation and H* desorption for electrocatalytic alkaline HER were simultaneously facilitated by Co(0)-MoS2, leading to HER activity superior to most of MoS2-based catalyst (overpotential: 28 mV at 10 mA/cm2; Tafel slope: 47 mV/dec).
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