Journal of Catalysis最新文献

{"title":"Plasmonic CuSe/CuTCPP S-scheme heterojunction for efficient CO2 photoreduction under visible-near-infrared light","authors":"Qiaozhen Xu, Wenhao Liu, Tao Lv, Hong Liu","doi":"10.1016/j.jcat.2025.116188","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116188","url":null,"abstract":"For maximal utilization of solar spectrum in CO₂ photoreduction, photocatalysts with a strong near-infrared (NIR) response are highly desirable. Herein, 2D/2D CuSe/CuTCPP heterojunctions were prepared by an electrostatic self-assembly strategy. The unique localized surface plasmon resonance (LSPR) effect of CuSe not only expands the light absorption range of the catalyst, but also facilitates the generation of hot electrons due to its excellent photothermal effect. In addition, the construction of S-scheme heterojunction between CuSe and CuTCPP effectively promotes the transport and separation of photogenerated carriers. Without any sacrificial agent, the CuSe/CuTCPP heterojunctions can selectively reduce CO₂ to CO under visible-NIR light. The highest CO generation rate of CuSe/CuTCPP reaches 198.4 μmol·g⁻¹·h⁻¹, corresponding to an apparent quantum efficiency of 0.21 % at 450 nm, 2.5 times higher than that of CuTCPP. Finally, the preliminary mechanisms of charge transfer and photoreaction are unraveled based on in-situ XPS and in-situ DRIFTS analysis. This study provides a new idea for efficient photocatalytic CO₂ reduction via coupling S-scheme heterojunction and non-noble-metal LSPR effect.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"9 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901590","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}

{"title":"Towards the computational design of single atom alloys for methane to ethylene conversion","authors":"Chengyu Zhou, Manish Kothakonda, Qing Zhao","doi":"10.1016/j.jcat.2025.116194","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116194","url":null,"abstract":"Direct conversion of methane to value-added chemicals has been a longstanding challenge in leveraging abundant natural gas resources due to unfavorable C–H bond activation and coke formation. We recently evaluated stability and reactivity of single atom alloys (SAAs) formed by atomically doping 3d-5d transition metals on Cu(111) as catalysts for direct methane conversion to C₂ hydrocarbons using density functional theory calculations. Here, to further develop catalyst design principles for this chemistry, we systematically evaluate kinetics of methane dehydrogenation and C–C coupling steps on ten promising Cu(111)-based SAAs and unearth descriptors that correlate with catalyst activity and selectivity. Our results show that ethylene formation is kinetically favored over ethane formation across all SAAs studied. Notably, catalytic activity of SAAs highly correlates with their selectivity for direct methane conversion to C₂ products, highlighting the synergy between dopant and host metal in enhancing methane activation and preference towards C–C coupling. In addition, we identify C₂H₄ adsorption energy as an effective descriptor that guides the SAA reactivity for methane activation to ethylene. Combining all analyses, we discover that iridium dispersed on copper (Ir/Cu) SAA stands out as a highly active and selective catalyst for methane to ethylene conversion. These findings pave the way for high-throughput screening of a vast SAA chemical space for the chemistry of methane transformation.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"23 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143905716","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}

{"title":"Selective regulation of oxygen transfer for green oxidation of n-butane under mild conditions: Performance and mechanism","authors":"Dongpo Li, Chao Xiong, Xingrui Zhao, Tianfu Yang, Yimo Wu, Peng Hu, Hongbing Ji","doi":"10.1016/j.jcat.2025.116187","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116187","url":null,"abstract":"Developing a green and efficient catalytic process for inert n-butane to produce Methyl-Ethyl-Ketone (MEK) is critical for the C4 chemical industry, however, realizing efficient activation of molecular oxygen under mild conditions to produce reactive oxygen intermediates and selectively transfer them to the target product still faces challenges. Herein, a synergistic catalytic strategy based on Proton-Coupled Electron Transfer (PCET) is developed, and the oxidation performance and mechanism of our Cu(TBBD) catalyst for air oxidation of n-butane in liquid-phase is evaluated and analyzed. Through meticulous optimization of process conditions, and comprehensive evaluation of reusability and scalability, this catalytic system shows excellent oxidation performance under mild reaction temperature. Besides, the reaction system is clean, and the products have high-value application prospects (MEK selectivity of 74 %, and acetic acid selectivity of 26 %). Thermodynamic and kinetic studies exhibit that the reaction system is endothermic and disordered, and can be well described by the zero-order dynamic with an apparent activation energy of 68.83 kJ/mol. The mechanism is revealed by some advanced instruments (<em>in-situ</em> IR, ESR, ESI-HRMS, etc.) and experimental derivations to be that oxygen molecular is efficiently synergistic activated by Cu(TBBD) and NHPI to generate alkoxy and peroxide free radical intermediates through the PCET process, which directly oxidize the substrate to produce the corresponding high-value chemicals. Moreover, DFT calculations further prove the rationality of the reaction mechanism. This work provides a reliable basis for reactor design and technology iteration of industrial oxidation of n-butane.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"34 1","pages":"116187"},"PeriodicalIF":7.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901595","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}

{"title":"Electrocatalytic conversion of benzaldehyde on Cu in alkaline media","authors":"Hongwen Chen, Jayendran Iyer, Yue Ma, Hui Chen, Sungmin Kim, Debra J. Searles, M. Ali Haider, Rachit Khare, Johannes A. Lercher","doi":"10.1016/j.jcat.2025.116164","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116164","url":null,"abstract":"Aqueous phase electrochemical hydrogenation (ECH) of benzaldehyde (BZ) on Cu/C in alkaline electrolytes (&lt;span&gt;&lt;span style=\"\"&gt;&lt;/span&gt;&lt;span data-mathml='&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\"&gt;&lt;mrow is=\"true\"&gt;&lt;mi mathvariant=\"italic\" is=\"true\"&gt;pH&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"&gt;&lt;svg aria-hidden=\"true\" focusable=\"false\" height=\"2.317ex\" role=\"img\" style=\"vertical-align: -0.582ex; margin-left: -0.089ex; margin-right: -0.132ex;\" viewbox=\"-38.5 -747.2 1430.5 997.6\" width=\"3.322ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;&lt;g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"&gt;&lt;g is=\"true\"&gt;&lt;g is=\"true\"&gt;&lt;use xlink:href=\"#MJMATHI-70\"&gt;&lt;/use&gt;&lt;use x=\"503\" xlink:href=\"#MJMATHI-48\" y=\"0\"&gt;&lt;/use&gt;&lt;/g&gt;&lt;/g&gt;&lt;/g&gt;&lt;/svg&gt;&lt;span role=\"presentation\"&gt;&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\"&gt;&lt;mrow is=\"true\"&gt;&lt;mi is=\"true\" mathvariant=\"italic\"&gt;pH&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;&lt;/span&gt;&lt;script type=\"math/mml\"&gt;&lt;math&gt;&lt;mrow is=\"true\"&gt;&lt;mi mathvariant=\"italic\" is=\"true\"&gt;pH&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/script&gt;&lt;/span&gt; varying between 8.6 and 12.3) forms both benzyl alcohol (BA), the C=O hydrogenation product, and hydrobenzoin (HB), the carbon–carbon coupling product, with high Faradaic selectivity towards C–C coupling (&gt;84 %) and high Faradaic efficiency. The rate-determining step for BA formation is the second H addition to the radical α-C of the surface hydroxy intermediate, while that for HB formation is the first H addition to the carbonyl O of an adsorbed BZ molecule. The subsequent C–C bond formation and second H addition (for HB formation) are fast. In the absence of BZ (i.e., in pure electrolyte), the rate-determining step for H&lt;sub&gt;2&lt;/sub&gt; evolution on Cu/C in alkaline conditions is the dissociation of H&lt;sub&gt;2&lt;/sub&gt;O on the electrode’s surface to form surface H* (i.e., the Volmer step). The H addition occurs primarily via a proton-coupled electron-transfer (PCET)-type mechanism wherein H&lt;sub&gt;2&lt;/sub&gt;O molecules act as the proton source, forming OH&lt;sup&gt;–&lt;/sup&gt; in the process. The high selectivity towards C–C coupling in alkaline media, compared to acidic media, is attributed to the slow H addition kinetics caused by the weaker protonation ability of H&lt;sub&gt;2&lt;/sub&gt;O compared to H&lt;sub&gt;3&lt;/sub&gt;O&lt;sup&gt;+&lt;/sup&gt;. Increasing electrolyte &lt;span&gt;&lt;span style=\"\"&gt;&lt;/span&gt;&lt;span data-mathml='&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\"&gt;&lt;mrow is=\"true\"&gt;&lt;mi mathvariant=\"italic\" is=\"true\"&gt;pH&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"&gt;&lt;svg aria-hidden=\"true\" focusable=\"false\" height=\"2.317ex\" role=\"img\" style=\"vertical-align: -0.582ex; margin-left: -0.089ex; margin-right: -0.132ex;\" viewbox=\"-38.5 -747.2 1430.5 997.6\" width=\"3.322ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;&lt;g fill=\"currentColor\" stroke=\"currentColor\"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"27 1","pages":"116164"},"PeriodicalIF":7.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901592","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}

{"title":"Visible light-induced catalytic syntheses of thioamides as biomass-based corrosion inhibitors for mild steel","authors":"Junda Chen, Jinzhu Chen","doi":"10.1016/j.jcat.2025.116180","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116180","url":null,"abstract":"It is a pioneering field for biomass valorization to construct high-efficient corrosion inhibitors for metal due to a big challenge and serious issue of metal corrosion during its industrial applications. Herein, we describe a visible light-induced three-component coupling of furfural, furylamine and (NH₄)₂S for biomass-based thioamide synthesis under mild conditions. The photo-catalyst for the coupling is well designed as Ni immobilized on a carbon-TiO₂ nanocomposite (Ni/C-TiO₂) with <em>in-situ</em> photo-generated hole (h⁺) and hydroxyl radical (·OH) as key oxidative species for thioamide formation. The photo-catalytic system is applicable to a variety of furfural-derived thioamides (20 examples). The anti-corrosive activities of typical thioamides are systematically investigated and compared with mild steel in 1.0 M HCl solution. Electron-rich furan ring (π-electrons system) with functional − NH − C(=S) − group (high electronic density of heteroatoms) endows these biomass-based thioamides high inhibition efficiencies towards the mild steel as mixed-type corrosion inhibitors for both cathode and anode.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"112 1","pages":"116180"},"PeriodicalIF":7.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901594","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}

{"title":"Computational exploration of codoped Fe and Ru single-atom catalysts for the oxygen reduction reaction","authors":"Haojun Jia, Chenru Duan, Gianmarco G. Terrones, Ilia Kevlishvili, Heather J. Kulik","doi":"10.1016/j.jcat.2025.116163","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116163","url":null,"abstract":"The Oxygen Reduction Reaction (ORR) is essential in a range of energy conversion and storage technologies, including fuel cells and metal–air batteries. Single-atom catalysts (SACs), characterized by isolated metal atoms especially in doped graphitic substrates, have emerged as promising ORR catalysts due to their unique electronic and geometric properties. We employ Virtual High-Throughput Screening (VHTS) with density functional theory and Machine Learning (ML) to explore the potential of codoped SACs with Fe and Ru centers for optimizing ORR reaction energetics. We also develop ML models, trained on VHTS data, that offer increased predictive accuracy of reaction energetics, surpassing the capabilities of conventional linear free energy relationship approaches. The results underscore codoping as an effective strategy for tuning SAC properties, enabling the rational design of high-performance ORR catalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"9 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897679","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}

{"title":"From pages to patterns: Towards extracting catalytic knowledge from structure and text for transition-metal complexes and metal-organic frameworks","authors":"Aditya Nandy","doi":"10.1016/j.jcat.2025.116174","DOIUrl":"10.1016/j.jcat.2025.116174","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116174"},"PeriodicalIF":6.5,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901593","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}

{"title":"Determining site requirements for reactive species in multi-site catalysis on metal surfaces using excluded areas","authors":"Ari F. Fischer","doi":"10.1016/j.jcat.2025.116179","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116179","url":null,"abstract":"Many metal-catalyzed reactions (e.g., hydrogenolysis, (de)hydrogenation, and hydro-deoxygenation) involve reactive species with molecular volumes that extend beyond the cross-sectional areas of exposed metal atoms. The kinetic behaviors of such reactions are well described by lattice-based models that account for adsorbates occupying multiple adjacent sites (i.e., exposed metal atoms). Site requirements are often inferred from the number of metal atoms an adsorbate coordinates to, which can underpredict the number of contiguous sites that are inaccessible to co-adsorbates by lateral repulsion. Here, we instead determine adsorbate site requirements from the surface areas they exclude from co-adsorbates. These areas are determined from adsorbate structures, optimized previously using density functional theory (DFT), by projecting their molecular volumes onto the surface plane (<em>A_S</em>) or by tracing their areas with a circular probe that represents co-adsorbates (<em>A_enc</em>). These excluded areas agree with those inferred from the experimentally measured saturation coverages of eight polyatomic adsorbates on Pt(1<!-- --> <!-- -->1<!-- --> <!-- -->1) and Ni(1<!-- --> <!-- -->1<!-- --> <!-- -->1). They predict a number of sites needed for ethane hydrogenolysis on Ir nanoparticles (two to three exposed Ir atoms) that is consistent with previous kinetic measurements and DFT calculations. The areas further estimate site requirements for benzene hydrogenation on Pt nanoparticles (six exposed Pt atoms) that accurately describe rate dependences on benzene pressure, under physically realistic benzene and H-adatom coverages and with adsorption enthalpies consistent with experimental benchmarks. Excluded areas therefore offer a practical and accurate way to determine site requirements in multi-site kinetic models, facilitating mechanistic studies and guiding ab initio catalyst design for reactions of bulky molecules that inevitably cover multiple contiguous surface atoms.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"76 1","pages":"116179"},"PeriodicalIF":7.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901596","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}

{"title":"Engineering amorphous MoS2/RGO hybrid nanoflowers with rich edge sites boost catalytic hydrogen generation","authors":"Bo Ma,&nbsp;Yong Zhang,&nbsp;Chunyong He","doi":"10.1016/j.jcat.2025.116178","DOIUrl":"10.1016/j.jcat.2025.116178","url":null,"abstract":"<div><div>To date, the electrolytic water splitting continues to be hindered by its high overpotential and sluggish kinetics of hydrogen evolution reaction (HER). Here, we design a new amorphous MoS₂/reduced graphene oxide hybrid nanoflowers (A-MoS₂/RGO NFs) architecture, in which two-dimensional (2D) few-layer MoS₂ nanosheets are grown on RGO, and assemble into three-dimensional (3D) nanoflowers. The amorphous MoS₂/RGO hybrid nanoflowers have plenty of exposed edge sites, which have been proved to be the catalytic active sites for HER. Besides, the distinctive and robust 3D architecture of amorphous MoS₂/RGO hybrid nanoflowers facilitate the HER by enhancing both mass transport and charge transfer kinetics. The amorphous MoS₂/RGO hybrid nanoflowers exhibit extraordinary HER performance with almost zero onset overpotential, small Tafel slope and extreme high electrochemical durability in wide pH range. The density functional theory (DFT) calculations demonstrate that the charge transfer from RGO to amorphous MoS₂, which increase the charge density of the edge-terminated Mo and S atoms. This unique electronic configuration facilitates efficient H₂O activation and dissociation, the subsequent H* adsorption and conversion processes, thereby significantly enhancing HER performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116178"},"PeriodicalIF":6.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893874","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}

{"title":"Palladium/rhodium-catalyzed four-component carbonylative difunctionalization of alkynes: Regio- and stereoselective esterification/selenylation to access β-selenyl acrylates","authors":"Fengxiang Zhu ,&nbsp;Huanan Wu ,&nbsp;Xiao-Feng Wu","doi":"10.1016/j.jcat.2025.116170","DOIUrl":"10.1016/j.jcat.2025.116170","url":null,"abstract":"<div><div>The development of efficient catalytic systems for 1,2-difunctionalization of alkynes remains a challenge due to limitations in substrate scope, selectivity, and step economy. Herein, we report a novel palladium/rhodium catalytic system for the four-component difunctionalization of alkynes, which enables concurrent incorporation of ester and selenyl groups with excellent regio- and stereoselectivity. This protocol utilizes readily available alkynes, phenols, carbon monoxide, and selenium reagents to construct β-selenyl acrylates in a single operation, demonstrating broad functional group tolerance and scalability.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116170"},"PeriodicalIF":6.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893877","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}