Journal of Catalysis最新文献

{"title":"Visible light-induced catalytic syntheses of thioamides as biomass-based corrosion inhibitors for mild steel","authors":"Junda Chen,&nbsp;Jinzhu Chen","doi":"10.1016/j.jcat.2025.116180","DOIUrl":"10.1016/j.jcat.2025.116180","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116180"},"PeriodicalIF":6.5,"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 ,&nbsp;Chenru Duan ,&nbsp;Gianmarco G. Terrones ,&nbsp;Ilia Kevlishvili ,&nbsp;Heather J. Kulik","doi":"10.1016/j.jcat.2025.116163","DOIUrl":"10.1016/j.jcat.2025.116163","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116163"},"PeriodicalIF":6.5,"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":"10.1016/j.jcat.2025.116179","url":null,"abstract":"<div><div>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 or by tracing their areas with a circular probe that represents co-adsorbates. 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) which accurately describes 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116179"},"PeriodicalIF":6.5,"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}

{"title":"Highly unsaturated oxygen promotes formaldehyde catalytic oxidation on the defective Co3O4 (111) surface: A DFT study","authors":"Xing Wang ,&nbsp;Jiajia Wang ,&nbsp;Dan Song ,&nbsp;Jianyong Feng ,&nbsp;Zhaosheng Li","doi":"10.1016/j.jcat.2025.116172","DOIUrl":"10.1016/j.jcat.2025.116172","url":null,"abstract":"<div><div>The active oxygen, which was generated through surface oxygen vacancy, showed high activities in HCHO catalytic oxidation by Co₃O₄ but why the active oxygen was so highly active remained unclear. In this study, density functional theory calculations were performed to unravel the role of active oxygen in HCHO catalytic oxidation on the Co₃O₄ (1<!--> <!-->1<!--> <!-->1) surface. The reaction paths of HCHO catalytic oxidation on perfect and defective Co₃O₄ (1<!--> <!-->1<!--> <!-->1) surfaces <em>via</em> three possible reaction mechanisms (MvK, E–R and L–H) were investigated. The results showed that, on the perfect Co₃O₄ (1<!--> <!-->1<!--> <!-->1) surface, the HCHO catalytic oxidation only followed the MvK mechanism. On the defective surface, the E–R and L–H mechanisms showed advantage over MvK mechanism because of the low energy barriers of C<img>H bond cleavage. Moreover, owing to the active O, the L–H mechanism showed great advantage because of the extremely low energy barrier of 0.1 eV for the first C<img>H bond cleavage. Further electronic structure calculations revealed that the high activity of active oxygen was mainly attributed to its high unsaturation degree, which induced a strong attraction of active oxygen to the H of HCHO and promoted C<img>H bond cleavage.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116172"},"PeriodicalIF":6.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893875","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":"Using machine learning to guide the synthesis of supported palladium catalysts with desired palladium dispersion","authors":"Kubra Tiras ,&nbsp;Burcu Oral ,&nbsp;Nazlinur Koparipek Arslan ,&nbsp;Sila Alemdar ,&nbsp;Ramazan Yildirim ,&nbsp;Alper Uzun","doi":"10.1016/j.jcat.2025.116176","DOIUrl":"10.1016/j.jcat.2025.116176","url":null,"abstract":"<div><div>Supported palladium catalysts are indispensable in a wide range of industries, including petrochemicals, pharmaceuticals, and the automotive sector. The dispersion of palladium within these catalysts, primarily determined by the average nanoparticle size, significantly influences both the catalytic properties and the utilization efficiency of palladium. This study explores the relationships between various catalyst synthesis parameters and the resulting Pd nanoparticle size/dispersion. We developed a machine learning (ML) model to guide future synthesis efforts aimed at achieving specific palladium dispersion levels. Data were collected from previous studies on supported Pd catalysts published between 2000 and 2023, encompassing 1543 distinct catalysts. Of these, 1295 data points were used to construct the ML model. Key synthesis parameters—such as synthesis method, metal loading, support type, support surface area, metal precursor, solvent, solvent pH, support’s point of zero charge, and calcination/reduction conditions—were identified as independent variables, while dispersion and average Pd nanoparticle size served as dependent variables. A random forest (RF) regression model was employed to predict dispersion (in %), validated through 5-fold cross-validation. The model achieved root mean squared errors (RMSE) of 9.5 (training) and 14.9 (testing) in Pd dispersion (in %) prediction. Experimental synthesis of new supported palladium catalysts using different synthesis parameters confirmed the model’s predictions, yielding an RMSE of 5.4. Additionally, data from the literature published in 2024 were also used to validate the model, the comparison resulted in an RMSE of 5.9. This ML approach offers significant potential for precisely controlling palladium dispersion during catalyst synthesis, moving beyond traditional trial-and-error methods. It holds a broad potential to significantly improve palladium utilization across a variety of industrial applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116176"},"PeriodicalIF":6.5,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885359","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":"Dual adsorbate mechanism in OER process achieved by the surface nitridation of the polydopamine modified electrodes","authors":"Chenglu Liang ,&nbsp;Longxia Wang ,&nbsp;Weiyi Li ,&nbsp;Xianbao Liu ,&nbsp;Jingyao Yin ,&nbsp;Zhiyan Feng ,&nbsp;Rong Guo ,&nbsp;Yang Liu ,&nbsp;Qianting Wang ,&nbsp;Chan Zheng","doi":"10.1016/j.jcat.2025.116169","DOIUrl":"10.1016/j.jcat.2025.116169","url":null,"abstract":"<div><div>The rate determining oxygen evolution reaction (OER) remains a challenge for hydrogen production through water electrolysis. Currently, OER mechanism of catalysts was regarded either following the adsorbate evolution mechanism (AEM) pathway, or the lattice oxygen oxidation mechanism (LOM) pathway. The LOM driven catalysts can directly form O-O bonds, thus accelerating the overall reaction. However, due to the dynamic formation of lattice oxygen, the leaching of uncoordinated metal ions usually leads to poor stability. Balancing the OER activity and stability in the LOM driven catalysts remained challenging. Herein, a catalyst electrode with emerged dual adsorbate mechanism (DAM) was constructed via the coordination of polydopamine and nitridation of a series of bimetallic oxides precursors (FeCo, FeNi, FeCu and CoCu). In the DAM driven electrode, both the metal center and lattice oxygen center participate in the OER cycles and formed the triangular *O-M-*<strong>O</strong> key intermediate, significantly reducing the energy barrier of the OER process, resulting in excellent OER activity and stability. The proposed DAM mechanism was verified by the experimental and theoretical calculation. Excellent OER performance was achieved in FeCo based electrodes with an over potential of 194/253 mV at a current density of 10/100 mA cm⁻² with greatly enhanced durability.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116169"},"PeriodicalIF":6.5,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885366","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":"Unraveling the role of CH3S* intermediates for efficient methane and hydrogen sulfide reforming over Mo/Al2O3 catalysts","authors":"Jundao Wu ,&nbsp;Zeai Huang ,&nbsp;Zhen He ,&nbsp;Rustem Zairov ,&nbsp;Xiaoting He ,&nbsp;Yue Huang ,&nbsp;Mengyao Fu ,&nbsp;Chengdong Yuan ,&nbsp;Oleg G. Sinyashin ,&nbsp;Ying Zhou","doi":"10.1016/j.jcat.2025.116168","DOIUrl":"10.1016/j.jcat.2025.116168","url":null,"abstract":"<div><div>The catalytic methane(CH₄) and hydrogen sulfide(H₂S) reforming (H₂SMR) represents a promising approach for producing high-value sulfur-carbon compounds and hydrogen without generating the greenhouse gas of CO₂. Despite its significant potential, the mechanistic understanding of interactions between CH₄ and H₂S remains contentious, posing substantial challenges for catalyst development. In this study, we employed a Mo/Al₂O₃ catalyst to elucidate synergistic conversion pathways between CH₄ and H₂S during H₂SMR. At 1173 K with a reaction duration of 0.5 h, conversion rates of CH₄ and H₂S reached 63.7 % and 59.2 %, respectively, accompanied by H₂ and CS₂ production rates of 688.8 μmol g⁻¹ min⁻¹ and 444.3 μmol g⁻¹ min⁻¹, respectively. Notably, the catalyst exhibited stable performance over 5 h without significant deactivation, in contrast to pure methane cracking reactions where CH₄ conversion rapidly declined from 43.6 % to 14.3 %. Through <em>in-situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with alternating CH₄/H₂S exposure experiments, we successfully tracked the synergistic conversion pathway on the Mo/Al₂O₃ catalyst. These investigations revealed that the formation of CH₃S intermediates serves as a critical step facilitating CS₂ generation. This mechanistic insight not only advances fundamental understanding of H₂SMR reaction pathways but also provides a rational foundation for designing optimized catalysts with enhanced stability and extended operational lifetimes. The identification of this intermediate-driven mechanism addresses previous controversies regarding CH₄-H₂S interactions and offers strategic guidance for developing efficient sulfur-resistant catalytic systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116168"},"PeriodicalIF":6.5,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890135","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}