Journal of Catalysis最新文献

{"title":"Examining generalizability of AI models for catalysis","authors":"Shih-Han Wang ,&nbsp;Hongliang Xin ,&nbsp;Luke E.K. Achenie ,&nbsp;Kamal Choudhary","doi":"10.1016/j.jcat.2025.116171","DOIUrl":"10.1016/j.jcat.2025.116171","url":null,"abstract":"<div><div>In this work, we investigate the generalizability of problem-specific machine-learning models for catalysis across different datasets and adsorbates, and examine the potential of unified models as pre-screening tools for density functional theory calculations. We develop graph neural network models for 12 different datasets for catalysis and then cross-evaluate their performance. Unified models include ALIGNN-FF, MATGL, CHGNet, and MACE. Pearson correlation coefficient analysis indicates that generalizability improves when similar adsorbates are used for training and testing or when a larger database is employed for training. Results demonstrate that while the accuracy of the unified models has room for improvement, their excellent performance in predicting the trend of adsorption energies can be a valuable pre-screening tool for selecting potential candidates prior to resource-intensive DFT calculations in catalyst design, thereby reducing computational expenses. The tools used in this work will be made available at: <span><span>https://github.com/usnistgov/catalysismat</span><svg><path></path></svg></span>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116171"},"PeriodicalIF":6.5,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237217","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":"CO2 oxidative dehydrogenation of ethane to ethylene: Reaction mechanism elucidation by tandem-reaction couplings","authors":"Yuxin Jin ,&nbsp;Ying Wang ,&nbsp;Chuanfu Wang ,&nbsp;Ming Chen ,&nbsp;Yun Zhao ,&nbsp;Daiqi Ye ,&nbsp;Limin Chen","doi":"10.1016/j.jcat.2025.116265","DOIUrl":"10.1016/j.jcat.2025.116265","url":null,"abstract":"<div><div>CO₂ oxidative dehydrogenation of ethane to ethylene (CO₂-ODHE) is a promising technology for carbon emission reduction in ethylene industry, which is a major part of the petrochemical industry. However, the complicated reaction networks significantly restricted researchers’ capability to fully understand the intrinsic catalytic behaviors and to design efficient catalysts. The reaction networks remain one of the major obstacles to explore highly efficient and durable catalysts for CO₂-ODHE reaction. Different from the usual researches where reaction mechanism investigations are fulfilled by relating catalyst performance to catalyst structure characterizations, this research provides a feasible reaction mechanism elucidation by qualitatively and quantitatively assessing the apparent reaction paths over the catalysts without catalyst structure characterizations. This approach can reveal ethane and CO₂ reaction routes in CO₂-ODHE by reaction couplings and enables the involvement percentage calculation of both ethane and CO₂ in the reaction networks. Through relative errors and gray correlation analysis, the approach’s application scope and rationality have been investigated and clarified. By revealing the reaction path, the proposed analysis approach can effectively guide the rational design of highly efficient catalysts for CO₂-ODHE and other similar complicated tandem-reaction systems. No catalysts research is involved in this paper.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116265"},"PeriodicalIF":6.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144229295","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":"Iridium single-atoms induced in situ H2O2 formation boosting the hydrothermal oxidation of methane to methanol with molecular O2","authors":"Mingyu Xie ,&nbsp;Xiyan Chen ,&nbsp;Yu-xin Ye ,&nbsp;Yanchang Chu ,&nbsp;Chao Cai ,&nbsp;Wei Zhang ,&nbsp;De-Li Chen ,&nbsp;Xiaohao Liu ,&nbsp;Le Yang","doi":"10.1016/j.jcat.2025.116270","DOIUrl":"10.1016/j.jcat.2025.116270","url":null,"abstract":"<div><div>Partial oxidation of methane to methanol has become a heavily investigated field. For cases using O₂ as oxidant, overoxidation is undesired and inevitable. To address this issue, we construct a single atom Ir₁/C catalyst with a unitary active site to achieve a high selectivity of methanol. Here we employed the O-adsorption modulation strategy to control the O₂ dissociation path on Ir site, where O₂ transforms into H₂O₂ on Ir single atoms (SAs) in contrast to Ir-O on Ir clusters. The subsequent decomposition of H₂O₂ into H₂O and *O on Ir SAs vastly decreases the barriers of CH₄ oxidation process, compared to the Ir clusters. Operando infrared spectroscopy demonstrates the observation of Ir-OOH, a strong evidence for the distinguished intermediate of Ir-HOOH. H₂O₂ was also detected and quantified as another important evidence for the formation of Ir-HOOH. Ir₁/C exhibited a much higher methanol productivity of 17mmol g⁻¹ than Ir_cluster/C (6mmol g⁻¹) under a feeding of 0.3 MPa CH₄ and 0.1 MPa air in water at 150 °C for 3 h, and the value raised to 31.3mmol g⁻¹ under 0.3 MPa CH₄. This work demonstrates that selectivity control and activity promotion in O-involved reaction can be realized via the O-adsorption modulation strategy.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116270"},"PeriodicalIF":6.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237211","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":"Exploiting MXenes properties for coking resistance of Ni catalyst in dry reforming of methane","authors":"Joshua O. Ighalo,&nbsp;AmirMohammad Ebrahimi,&nbsp;Morgen L. Smith,&nbsp;Ahmed Al Mayyahi,&nbsp;Haider Almkhelfe,&nbsp;Davood B. Pourkargar,&nbsp;Placidus B. Amama","doi":"10.1016/j.jcat.2025.116268","DOIUrl":"10.1016/j.jcat.2025.116268","url":null,"abstract":"<div><div>The development of coke-resistant catalysts for dry reforming of methane (DRM) is critical for sustainable syngas production. To suppress coking, this study investigates the use of Ti₃C₂T_x and Nb₂CT_x MXenes as support for Ni catalysts in DRM and benchmarked their performance with conventional catalysts (Ni/γ-Al₂O₃, Ni/MgAl₂O₄, and Ni/SiO₂). The MXenes were etched using NH₄HF₂, and a 10 wt% Ni loading on the supports was achieved via wet impregnation synthesis. Ni/Nb₂CT_x showed the highest H₂ consumption (10.4 mmol_H2/g_cat). DRM was conducted at 700 °C using a feed ratio of CH₄/CO₂ of 1:1 and a high space velocity (90,000 ml/g_cat h). Unlike the other catalysts, Ni/Nb₂CT_x pre-reduced at 500 °C exhibited a low normalized coking rate (4.41 µg_coke/mmol_CH4), a high overall reaction rate (104 ± 13 mmol/g_Ni.min), and the highest turnover frequency at 16.7 s⁻¹. The apparent CO₂ reaction rate at these conditions was similar to the CH₄ rate, suggesting that the low coking rate was due to the efficient utilization of dissociated oxygen. Molecular dynamics (MD) simulations performed on NbC(111) and TiC(111) surfaces at 700 °C and atmospheric pressure reveal that the efficient utilization was mediated by rapid oxygen spillover. The average oxygen velocity from the simulations was slightly higher on NbC (0.0969 Å/fs) than on TiC (0.0961 Å/fs). Both MXene supports are transformed to stable oxycarbides during DRM, and Nb₂CT_x was stable for 50 h TOS. This investigation not only highlights the potential of Ni/Nb₂CT_x as a coke- and sintering-resistant catalyst but also demonstrates the role of MXenes supports in the DRM process.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116268"},"PeriodicalIF":6.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219206","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":"Effect of 1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) on the ruthenium-catalyzed transfer hydrogenation of ketones","authors":"Sylwia Ostrowska ,&nbsp;Riku Saito ,&nbsp;Tommaso Ruggiero ,&nbsp;Kristof Van Hecke ,&nbsp;Cezary Pietraszuk ,&nbsp;Steven P. Nolan","doi":"10.1016/j.jcat.2025.116248","DOIUrl":"10.1016/j.jcat.2025.116248","url":null,"abstract":"<div><div>We have examined the effect of the addition of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) on the Transfer Hydrogenation (TH) reaction of ketones catalyzed by [Ru(CO₃)(NHC)(<em>p</em>-cymene)] complexes. We disclose a series of air-stable ruthenium-NHC complexes of type [Ru(CO₃)(NHC)(p-cymene)]·(HOC(H)(CF₃)₂). The bulky and less sterically demanding N-Heterocyclic Carbene (NHC) ligands greatly influence the yields of the transfer hydrogenation of the tested ketones. The reactivity studies involving complexes containing HFIP reveal TH reactions of ketones can be performed at lower temperature and lower catalyst loading compared to state-of-the-art conditions. Base-free TH of ketones in the presence of [Ru(CO₃)(NHC)(p-cymene)]·(HOC(H)(CF₃)₂) is also possible.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116248"},"PeriodicalIF":6.5,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211602","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":"Tuning plasmonic reactivity: Influence of nanostructure, and wavelength on the dimerization of 4-NTP","authors":"M. Condorelli ,&nbsp;A. Brancato ,&nbsp;C. Longo ,&nbsp;M. Barcellona ,&nbsp;M.E. Fragalà ,&nbsp;E. Fazio ,&nbsp;G. Compagnini ,&nbsp;L. D’Urso","doi":"10.1016/j.jcat.2025.116267","DOIUrl":"10.1016/j.jcat.2025.116267","url":null,"abstract":"<div><div>Hot electrons generated in plasmonic nanoparticles are considered a key candidate for their ability to promote reduction reactions of organic molecules selectively. Such chemical transformations can occur when molecules are adsorbed on the surface of plasmonic nanoparticles interacting with an external incident electromagnetic field. The so-called localized surface plasmon resonance phenomenon, induced by the electromagnetic field, is responsible for the generation of energetic electrons which in turn can be transferred to the molecule, causing its reduction. It is known that such plasmon-induced hot carrier reactions mainly occur in proximity of the so-called hot spots, areas of the plasmonic particle with enhanced electromagnetic field.</div><div>In this study, we discuss the photocatalytic performances via hot-electron transfer of three different silver nanoplatforms (nanospheres, nanoplatelets, and nanoflowers) for the conversion of 4-nitrothiophenol (4-NTP) to dimercaptoazobenzene (DMAB). The reaction was monitored via surface-enhanced Raman spectroscopy (SERS), irradiating the sample with a 532 nm or a 785 nm laser line. In both cases, we noticed a clear correlation between particle morphologies and reaction kinetic, useful for identifying the more favorable silver nanocatalyst. Moreover, measurements carried out by the 785 nm laser radiation revealed an unexpected conversion of 4-NTP to 4-aminothiophenol (4-ATP) on silver nanoflowers in the absence of reducing agents. This innovative approach opens up the interesting possibility of developing plasmonic nanoparticle-based catalysts with sustained performance while reducing the presence of chemical reactants and providing an alternative and cleaner synthetic chemical route.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116267"},"PeriodicalIF":6.5,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144193085","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":"Tuning oxygen vacancy defects in VOx/Ce1-xLaxO2−δ nanorod catalysts through La doping for selective methanol oxydehydrogenation to dimethoxymethane","authors":"Naseer Ahmad Safi,&nbsp;Habib Ullah,&nbsp;Guilin Liu,&nbsp;Feng Xin","doi":"10.1016/j.jcat.2025.116264","DOIUrl":"10.1016/j.jcat.2025.116264","url":null,"abstract":"<div><div>Methanol oxydehydrogenation to produce dimethoxymethane (DMM) and its use as a key feedstock for the synthesis of PODE_3-5, an emerging diesel additive, represents a promising strategy for mitigating diesel exhaust emissions. However, achieving high methanol conversion with high selectivity for DMM remains a significant challenge at low temperatures. Herein, a La-doped ceria-supported vanadia (VO_x/Ce_1-xLa_xO_2-δ) nanorod catalyst was prepared by a one-step hydrothermal method to create sufficient asymmetric oxygen vacancies. Diverse techniques were employed to comprehensively analyze the catalyst structure and active sites. The results indicate that the generated oxygen vacancies not only activate oxygen species but also accelerate the cleavage of O–H and C–H bonds alongside V⁵⁺ active site within the adsorbed methanol during the methanol oxydehydrogenation reaction. The VO_x/Ce_0.8La_0.2O_2-δ catalyst demonstrated superior catalytic efficiency, achieving 81 % methanol conversion and 95 % selectivity for dimethoxymethane under atmospheric pressure and at 200 °C in a fixed-bed reactor.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116264"},"PeriodicalIF":6.5,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144188983","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 proton-coupled electron transfer engineering between CuxIny alloy and polyoxometalate medium for efficient CO2 electroreduction to CO","authors":"Wencong Sun ,&nbsp;Chunxiang Li ,&nbsp;Yuehua Tai ,&nbsp;Li Zhou ,&nbsp;Wenxue Tian ,&nbsp;Shumiao Li","doi":"10.1016/j.jcat.2025.116254","DOIUrl":"10.1016/j.jcat.2025.116254","url":null,"abstract":"<div><div>Polyoxometalates (POMs) are promising electrolyte additives to promote the electrocatalytic CO₂ reduction reaction (ECO₂RR) at the electrode/electrolyte interface, but the pure metal electrode’s severe oxidation caused by POM’s proton-coupled electron transfer (PCET) characteristic remains unfavorable for ECO₂RR. Herein, three new Cu_xIn_y alloys with different element ratios (1:1, 2:3, and 1:3) were prepared by the one-step reduction method. The effects of PCET behavior between the as-prepared alloys and a Keggin-type POM (PV₂MoW₉) on ECO₂RR performance were explored. Among prepared alloys, Cu₁In₃ shows the highest Faradic efficiency of CO (FE_CO) of 95.3% at −0.25 V (vs. RHE) in POM medium. The experimental results suggest greatly enhanced reaction kinetics in the presence of PV₂MoW₉. <em>In-situ</em> surface enhanced Raman data reveal the highly affected performance of ECO₂RR by the sequential PCET behavior between PV₂MoW₉ and Cu_xIn_y alloy. As a “sacrificial agent”, the initially generated In₂O₃ assists in segregating Cu atoms on the alloy surface, thereby promoting the process ECO₂RR → CO. From the perspective of electrode-electrolyte interaction, this work proposes a new strategy to adjust the ECO₂RR reaction pathway through rational design of alloy element composition.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116254"},"PeriodicalIF":6.5,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144188985","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":"Role of support in phenol hydrodeoxygenation over supported Pd catalysts: Insights from first-principles based microkinetic modelling","authors":"Dipika Rajendra Kanchan,&nbsp;Arghya Banerjee","doi":"10.1016/j.jcat.2025.116266","DOIUrl":"10.1016/j.jcat.2025.116266","url":null,"abstract":"<div><div>Catalytic Hydrodeoxygenation (HDO) of biomass pyrolysis-derived bio-oil is a critical step for reducing oxygen content in the bio-oil, before its utilisation as a fuel. In this regard, HDO of bio-oil model compounds have been investigated over numerous supported metal catalysts, but the role of support on the catalytic activity has been largely ignored. In this work, the reaction mechanism for HDO of phenol – a bio-oil model compound was investigated on Pd/Al₂O₃, Pd/ZrO₂ and Pd/TiO₂ catalysts. Comprehensive reaction map and energetics of the multiple reaction pathways for phenol activation to benzene and cyclohexanone were elucidated using first-principles Density Functional Theory (DFT) calculations. The metal-support interface provides a unique site for the adsorption of the reactants and the intermediates, which alter the reaction mechanism and consequently the product distribution. Over TiO₂ and ZrO₂ supports, phenol adsorbs on the Pd-support interface with the phenolic O binding to oxophilic cation of the oxide support and ring carbon to Pd, thereby weakening the C_aryl-O bond and facilitating its cleavage to form benzene. In the case of Al₂O₃, phenol adsorbs only through the ring carbon on the Pd, which results in ring-hydrogenated products like cyclohexanone. A microkinetic analysis revealed the direct deoxygenation pathway to benzene to be favoured over Pd/ZrO₂ and Pd/TiO_2, while cyclohexanone production via a phenoxy intermediate was favoured on Pd/Al₂O₃, in agreement with experimental results.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116266"},"PeriodicalIF":6.5,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144188982","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":"A highly stable metallosalen-based metal–organic framework electrocatalyst for versatile oxidative organic transformations","authors":"Lei-Yan Lyu ,&nbsp;Fa-Xue Ma ,&nbsp;Xin-Ling Xie ,&nbsp;Meng-Jiao Sun ,&nbsp;Tao Huang ,&nbsp;Teng Zhang","doi":"10.1016/j.jcat.2025.116252","DOIUrl":"10.1016/j.jcat.2025.116252","url":null,"abstract":"<div><div>Production of epoxides and aldehydes as key intermediates for organic synthesis usually suffers from the consumption of toxic, corrosive or explosive oxidants. Electrochemical oxidation of alkenes and alcohols have been proposed as alternative green, atom-economic and sustainable synthetic methods, yet the lack of efficient electrocatalysts severely limits potential industrial applications due to the low selectivity and poor stability. We herein present the synthesis of FICN-24, a chemically stable metal–organic framework constructed from Ni₈-pyrazolate secondary building units and Mn(salen)-derived ligands, as an active and selective electrocatalyst for alkene epoxidation and alcohol oxidation reactions. FICN-24 showed high yields and selectivity up to &gt; 90 % towards the desired epoxide and aldehyde products in the electrochemical oxidation of a broad scope of alkene and primary alcohol substrates, respectively, and retained its structural integrity and catalytic activity upon recycling. This work establishes MOF-based electrocatalysis as a promising platform for selective organic transformations, advancing sustainable synthesis in alignment with green chemistry principles.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116252"},"PeriodicalIF":6.5,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176707","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}