Journal of Catalysis最新文献

{"title":"Zn modulating the metal support interaction to promote the sintering resistance of hydrotalcite-derived NiZnAl catalyst for methane cracking","authors":"Mengjie Cao, Shuangde Li, Shikun Wang, Weichen Xu, Xin Zhou, Guangxin Ma, Yunfa Chen","doi":"10.1016/j.jcat.2025.116103","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116103","url":null,"abstract":"Developing an efficient and environmentally friendly catalyst is important for the production of pure H₂ and carbon nanomaterials. Catalytic cracking of methane offers the possibility of producing these high-value products. For this reason, stabilizing the surface active sites of activated methane by modulating the interaction between metal and support has attracted much attention in the development of hydrotalcite-derived NiAl catalysts. Hence, the influence of Zn content and cracking temperature on the structure and performance of hydrotalcite-derived NiZnAl methane cracking catalysts were investigated. It is shown that alloying Zn with Ni reduces the electron density near Ni atoms, promotes the reduction of mixed metal oxides, producing strong interactions between Ni and support, thus improving the stability of the catalyst during methane decomposition. Thus, this strong interaction between Ni and support stabilized the Ni particle size and inhibited the sintering of Ni during the reaction. The Ni_2.7Zn_0.3Al can maintain a H₂ yield of more than 60 % over a 600 min reaction time at 600 °C. TEM analysis showed that the strong metal support interaction changed the morphology of the deposited carbon, maintained the balance between carbon diffusion and CH₄ dissociation, provided more growth sites for carbon nanotubes, and also prevented the rapid deactivation of the catalysts because of carbon encapsulation. This article may provide guidance for the design of Ni-based methane cracking catalysts with excellent stability.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"33 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713371","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":"Exploring the electronic metal-support interactions in platinum-deposited cobalt oxide catalysts for benzene combustion: A comparison of Pt nanoparticles and site-isolated Pt atoms","authors":"Jiangwei Ni, Jia Chen, Jinxu Fang, Zhiwei Huang, Mingshuo Tian, Qiqi Zhou, Wen Chen, Juanjuan Gong, Junhong Chen, Shuangning Gan, Xinlong Liao, Xiaomin Wu, Huazhen Shen, Huawang Zhao, Guohua Jing","doi":"10.1016/j.jcat.2025.116100","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116100","url":null,"abstract":"Insight into metal-support interactions at the nanoscale is of prominent significance in the development of efficient catalysts for volatile organic compound (VOC) abatement. This study investigates catalysts with distinct Pt active centers including Pt nanoparticles (Pt_NP) and single-atom Pt (Pt₁) supported on Mn-Co₃O₄ and reveals their electronic metal-support interaction characteristics. Benzene combustion tests show a contrasting trend exhibited by these two representative samples. Characterization techniques confirm that the superior performance of Pt_NP/Mn-Co₃O₄ stems from promotive electronic interaction. The effective charge transfer enhances reducibility and oxygen activation, coupled with the excellent benzene adsorption capacity of Pt_NP. However, the inhibitive role of Pt₁ in Mn-Co₃O₄ hinders the lattice oxygen mobility and leads to undesirable performance. Mechanistic insights elucidate the EMSI-induced benefits of being less prone to surface species poisoning, along with detailed reaction mechanisms and benzene decomposition route. This EMSI-dependent understanding of benzene combustion behavior offers valuable insights into the rational design of Pt-based catalysts for benzene abatement.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"125 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713372","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":"Stable bio-inspired Mn4O4 cubic molecular photo catalyst for effective visible light-driven C–H direct trifluoromethylation","authors":"Shujing Li, Ke Li, Wenjie Shi, Keren He, Han Xie","doi":"10.1016/j.jcat.2025.116106","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116106","url":null,"abstract":"Inspired by the natural oxygen-evolving complex of photosystem II with a cubic Mn₄CaO₅ cluster, there is relatively little research on photo catalysts that closely resemble the cubic Mn₄CaO₅ cluster. Therefore, the development of mixed-valence Mn₄CaO₅ simulacrums has sparked great interest. Herein, we successfully obtained a Mn₄O₄ cubic cluster with [Mn₄(<em>mbm</em>)₄(CH₃CH₂OH)₄Br₄]·[Mn₄(<em>mbm</em>)₄(CH₃CH₂OH)₃(H₂O)Br₄] (<strong>Mn₄Br</strong>) by using MnBr₂ and 1-Me-benzo[d]imidazol-2-yl)methanolate (H<em>mbm</em>) with its structure determined by single crystal crystallography. The Mn₄O₄ cubic cores consists of an octahedral Mn(II) center chelated by the alkoxide oxygen and imidazole nitrogen atoms from monoanionic <em>mbm</em>⁻ and coordinated by alcohol/H₂O and bromide ion. <strong>Mn₄Br</strong> was found to exhibit activity for trifluoromethylation reaction under visible light. The oxidization of <strong>Mn₄Br</strong> under I₂ solution led to the formation of mix-valent <strong>Mn₄Br-I₂</strong> with smallest sizes, which exhibited improved much higher activity for the C–H activated trifluoromethylation reaction due to the much higher redox performance as well as a lower charge-transfer resistance. This study provides a new and efficient strategy for the synthesis of Mn₄CaO₄ simulacrum structures with mixed valent states and develops its application in photocatalytic organic synthesis.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"3 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713370","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":"Corrigendum to “From cyclohexanol to aniline: A novel dehydrogenation-amination-dehydrogenation strategy based on Pt-based catalyst” [J. Catal. 429 (2024) 115233]","authors":"Shengchao Jia, Xiaohui Liu, Yong Guo, Lin Dong, Zupeng Chen, Yanqin Wang","doi":"10.1016/j.jcat.2025.116085","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116085","url":null,"abstract":"In this corrigendum, we report a correction to the XRD patterns in Figure 1a in our published paper entitled “<strong>From cyclohexanol to aniline: A novel dehydrogenation-amination-dehydrogenation strategy based on Pt-based catalyst</strong>” (J. Catal. 429 (2024) 115233).","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"37 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695807","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":"Elucidating the correlation between active species and branch distribution of polyethylene in Ziegler-Natta catalysis","authors":"Tao Guo ,&nbsp;Chuanding Dong ,&nbsp;Xiaokai Cheng ,&nbsp;Jingdai Wang ,&nbsp;Yongrong Yang ,&nbsp;Wei Li","doi":"10.1016/j.jcat.2025.116092","DOIUrl":"10.1016/j.jcat.2025.116092","url":null,"abstract":"<div><div>The ethylene/<em>α</em>-olefin copolymers synthesized by Ziegler-Natta catalysts generally exhibit much higher Short-Chain Branch (SCB) concentration in the low-molecular-weight fraction, which hampers the mechanical properties of the final products. Herein, we investigate the mechanism underlying the origin of SCB distribution at a molecular level. We design a spherical catalyst combining two alcohols with different mobility, after which a second titanation step with incremental TiCl₄ loading is applied to drive the migration of alcohol molecules. This migration induces not only the escape of alcohols from the catalyst surface but also the coordination of alcohols with Ti centers, which regulates the mobility of active species on the catalyst surface. We demonstrate that the aggregation behavior of Ti species is directed by their bonding to the MgCl₂ surface, where either TiCl₃-like clusters or isolated Ti³⁺ sites can be preferentially synthesized during triethylaluminium activation. Further polymerization results combined with electron paramagnetic resonance analysis show that TiCl₃-like clusters and the “dormant” active species contribute to the uniform SCB distribution over different molecular weights, whereas the predominated isolated Ti³⁺ sites on the MgCl₂ (110) plane concentrate the SCB in the low-molecular-weight fraction of the synthesized polyethylene. Taken together, we reveal a correlation between polymer branching distribution and catalytic structures, and show that the latter can be regulated by tailoring the migration of alcohols.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116092"},"PeriodicalIF":6.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695887","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":"Self-Promoting NO electrochemical reduction via N-N coupling by Surface-Adsorbed *NH intermediates on Mo2C nanosheets","authors":"Xiang Huang, Xiangting Hu, Jiong Wang, Hu Xu","doi":"10.1016/j.jcat.2025.116097","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116097","url":null,"abstract":"Electrochemical reduction of NO (NORR) to ammonia has gained significant attention due to its potential in both electrocatalytic denitrification and ammonia synthesis. Transition-metal carbides (TMCs), with their high reactivity toward NO activation, have emerged as promising candidates for NORR electrocatalysts. However, their exceptional catalytic performance in the hydrogen evolution reaction (HER)—a major competing process—may hinder the Faradaic efficiency of NH₃ production. Interestingly, recent experimental studies have shown that NORR almost completely suppresses HER on Mo₂C nanosheets under typical HER operating conditions, but the underlying mechanism remains unclear. Here, using state-of-the-art grand canonical density functional theory calculations, we reveal the atomic-level reaction mechanism of NORR on TMCs by taking experimentally reported Mo₂C as a prototype. Our findings show that within the potential range of −0.3 V to 0 V vs. RHE, the Mo₂C surface becomes nitrogenated by a monolayer of chemisorbed *NH intermediates, leading to poisoning of the surface. However, these adsorbed surface *NH intermediates can effectively adsorb NO molecules through an N-N coupling mechanism, facilitating their electrochemical reduction to NH₃ with fast reaction kinetics and favorable thermodynamics, thereby showing a self-promoting catalytic mechanism. Importantly, these *NH intermediates significantly suppress HER through strong electrostatic repulsion with incoming protons (or adjacent *NH species), leading to barriers exceeding 2 eV for both Heyrovsky and Tafel reactions. Our calculations provide crucial insights into the decisive role of *NH intermediates in promoting NH₃ production while suppressing H₂ generation, thus providing valuable guidance for the rational design of TMC-based NORR electrocatalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"71 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695889","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":"Quantifying π-electron delocalization as a universal descriptor for ORR activity in MN4 catalysts","authors":"Miao-Ying Chen, Jiabo Le, Hao-Ran Wu, Wei-Dong Li, Jia-Nan Zhang, Bang-An Lu","doi":"10.1016/j.jcat.2025.116093","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116093","url":null,"abstract":"The development of high-performance transition metal and nitrogen co-doped carbon (M−N−C) catalysts for the oxygen reduction reaction (ORR) hinges on identifying robust and quantitative descriptors for catalytic activity. In this study, we introduce the π-electron delocalization factor (Δπ) in the carbon basal plane as a universal and quantitative descriptor for ORR activity. By combining experimental data and density functional theory (DFT) calculations, we demonstrate that Δπ systematically tunes the <em>d</em>-orbital energy levels of MN₄ active sites, particularly the d<em>_z</em>² orbital, which governs the adsorption of oxygen intermediates and influences the rate-determining step of the ORR. A linear correlation between Δπ and ORR kinetics across different metal centers (Fe, Mn, Co, Ni) highlights the pivotal role of π-electron delocalization in optimizing the metal–oxygen interaction. This study provides a novel framework for quantifying catalytic performance and offers an efficient strategy for the rational design and screening of next-generation M−N−C catalysts with enhanced ORR activity.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"27 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678088","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":"Theoretical insights and predictions: Photocatalytic functionalization of C(sp3)-H bonds in methane using [W10O32]4-","authors":"Yu-Jiao Dong, Bo Zhu, Zhong-Min Su, Wei Guan","doi":"10.1016/j.jcat.2025.116101","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116101","url":null,"abstract":"Methane activation catalyzed by [MW₉O₃₂]^n- (n = 3–5) and [MW₅O₁₉]^m- (m = 1–3) was investigated through Density Functional Theory (DFT) calculations. We identified the key active species, active site, and reaction mechanism by studying the model reaction of methane hydroalkylation catalyzed by [W₁₀O₃₂]^4-. Systematic comparisons across modified polyoxometalates (POMs) revealed multiple electronic and structural descriptors governing methane activation efficiency. A key discovery involves the role of photoinduced surface-bridging oxygen holes in [W₁₀O₃₂]^4-, which serve as active sites for cleaving the inert C(sp³)<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>H σ-bond. While other POMs, including [W₆O₁₉]^2-, [PW₁₂O₄₀]^3-, and [P₂W₁₈O₆₂]⁶ ^--, also exhibit methane-activating oxygen holes, their requirement for higher-energy UV excitation (compared to the visible-light-responsive [W₁₀O₃₂]4^-) likely explains the latter’s broader utility in organic synthesis. Electronic structure analysis uncovered a near-linear correlation between triplet POM β-LUMO energies and C(sp³)<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>H activation barriers. Crucially, the negative charge density of POMs inversely regulates β-LUMO energetics: lower anionic charges correspond to reduced β-LUMO energy levels and consequently lower activation barriers. This structure–activity relationship implies that strategic charge modulation in POM architectures can fine-tune frontier molecular orbital levels, thereby controlling catalytic performance in methane functionalization. Based on these principles, we propose the low-charge metal-substituted POM [ReW₅O₁₉]^- as a promising candidate for X<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>H bond activation (X = S, C, N, O).","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"21 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678090","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":"Halogen-free and solvent-free CO2 cycloaddition via adjusting the types of surface defect and doped metal on the metal-doped M/AlOOH catalysts","authors":"Lixuan Ma, Na Li, Baojun Wang, Maohong Fan, Lixia Ling, Riguang Zhang","doi":"10.1016/j.jcat.2025.116099","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116099","url":null,"abstract":"The development halogen-free, solvent-free heterogeneous catalysts for CO₂ cycloaddition with epoxides remains critical, as conventional homogeneous systems face challenges in product separation and leave halogen residues. This work addresses these limitations by designing a series of halogen-free M/AlOOH catalysts with different types of doped metal M and surface defects, to optimize CO₂ cycloaddition with ethylene oxide (EO) by the regulation of acid-base properties. Theoretical and experimental analyses reveal that Lewis acid-base pairs composed of M∙∙∙V_H and M∙∙∙V_OH could stabilize the ring-opening intermediates (LO/LC) and promote EO ring-opening over M/AlOOH catalysts. Crucially, activated CO₂^δ− species mimic halogen’s nucleophilic role in attacking EO, with catalytic activity exhibiting an inverted volcano relationship to the Bader charge of CO₂^δ− species, Optimal performance occurs when the CO₂^δ− charge within 0.23 ∼ 0.55 e, where enhanced nucleophilicity drives cycloaddition. This study establishes a rational strategy for designing sustainable heterogeneous catalysts that eliminate halogens and solvents while maintaining high activity, offering a blueprint for green catalytic systems in CO₂ utilization.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"97 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695888","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":"An urgent call for robust statistical methods in reliable feature importance analysis across machine learning","authors":"Yoshiyasu Takefuji","doi":"10.1016/j.jcat.2025.116098","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116098","url":null,"abstract":"Accurate analytical outcomes in machine learning are contingent on error-free calculations and a solid understanding of foundational principles. A notable challenge arises from the lack of ground truth values for validation, complicating the assessment of feature importance, especially when employing linear models with parametric assumptions. This paper critiques the use of Pearson correlation and feature importances derived from Gradient Boosting Regressor (GBR), emphasizing their limitations in analyzing nonlinear and nonparametric data. We propose robust statistical methods, such as Spearman’s correlation and Kendall’s tau, as alternatives for capturing complex relationships while providing essential directional information. Additionally, attention to Variance Inflation Factor (VIF) is crucial for mitigating feature inflation. By addressing these concerns, researchers can achieve more reliable analyses and deeper insight into variable relationships.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"35 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695890","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}