Journal of Catalysis最新文献

{"title":"Surface hydroxyl on TiO2 promoted formation of α-C radical and oxaziridine intermediates in aerobic oxidation of amine into oxime","authors":"Huacheng Ying ,&nbsp;Zeyu Wen ,&nbsp;Jia Yao ,&nbsp;Mowei Zhou ,&nbsp;Yongtao Wang ,&nbsp;Haoran Li","doi":"10.1016/j.jcat.2025.116111","DOIUrl":"10.1016/j.jcat.2025.116111","url":null,"abstract":"<div><div>Constructing N−O bond in amines via aerobic oxidation is of high interest for producing cyclohexanone oxime; however, the mechanism remains disputed. Concerning TiO₂/NHPI co-catalyzed aerobic oxidation of cyclohexylamine, here a convincing mechanism involving α-C radical and oxaziridine as key intermediates is demonstrated. All the evidences from electron paramagnetic resonance, mass spectrometry, and product analysis with methylated substrates lead to the same story about the mechanism, where both radical translocation of cyclohexylamino radical and epoxidation of 1-hydroperoxycyclohexylamine are mediated by double proton transfer and are the key to convert amine into oxime. Near IR analysis indicate that surface hydroxyl groups on TiO₂ facilitate the double proton transfer process. Here the unveiled role of surface hydroxyl on TiO₂ highlights its potential for broader applications in amine activation. Additionally, the well-established radical mechanism provides valuable insight into the construction of N−O bonds in amines.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116111"},"PeriodicalIF":6.5,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734400","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":"Boosting CO2 electroreduction to ethylene via CoII-porphyrin regulated Cu2O/Cu nanocomposite","authors":"Yanyan Zhang ,&nbsp;Lingling Peng ,&nbsp;Xinming Li ,&nbsp;Xiaohu Zhang ,&nbsp;Renjie Li ,&nbsp;Yuexing Zhang ,&nbsp;Tianyou Peng","doi":"10.1016/j.jcat.2025.116109","DOIUrl":"10.1016/j.jcat.2025.116109","url":null,"abstract":"<div><div>CO₂ electroreduction (CO₂ER) into high value-added chemicals or fuels is of great significance to solve the current energy shortage and realize the carbon cycle. Although there are reports that Cu-based CO₂ER catalysts can achieve multicarbon products, the influence of the microenvironment of Cu-based catalysts on their valence states, interface and CO₂ER performance still deserve further investigation. Herein, a Co^II-porphyrin derivative (<em>m</em>-CoTPyP) is used to decorate on Cu₂O/Cu nanoparticles with Cu⁺/Cu⁰ mixed valence states and Cu₂O/Cu interface for constructing a novel CoTPyP-Cu₂O/Cu composite, where <em>m</em>-CoTPyP as ultrathin layer on Cu₂O/Cu nanoparticles can not only efficiently promote the adsorption/activation of CO₂ and the formation of *CO on the active sites by regulating the microenvironment <em>via</em> H-bonding, but also improve the stability of Cu valence states. Moreover, the Cu⁺/Cu⁰ mixed valence states and abundant Cu₂O/Cu interfaces of the Cu₂O/Cu nanoparticles significantly enhance the electron transfer rate and C<img>C coupling kinetics. Specifically, the CoTPyP-Cu₂O/Cu(1:15) delivers an ethylene (C₂H₄) Faraday efficiency up to 71 % and excellent stability (&gt;50 h). This work provides a new perspective on the structural design of CO₂ER catalyst with synergistic active sites, high Faraday efficiency and selectivity of C₂H₄ by regulating the microenvironment.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116109"},"PeriodicalIF":6.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723881","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":"Passivation of Brønsted acid sites at external surfaces of MFI zeolites and effects on propene oligomerization catalysis","authors":"Ricem Diaz Arroyo,&nbsp;Rajamani Gounder","doi":"10.1016/j.jcat.2025.116107","DOIUrl":"10.1016/j.jcat.2025.116107","url":null,"abstract":"<div><div>Alkene oligomerization to higher molecular weight products is a useful route for converting light hydrocarbon gases to liquid transportation fuels. Heterogeneous distributions of Brønsted acid sites in zeolites, arising from spatial gradients of Al centers in intracrystalline regions and at unconfined extracrystalline surfaces, influence rates, selectivity, and deactivation for acid-catalyzed reactions. Here, we synthesized core@shell materials composed of Al-MFI cores and Si-MFI shells of varying thickness, characterized crystallite-scale Al distributions by elemental analysis and electron microscopy, and quantified fractions of external acid sites by mesitylene benzylation rate constants. Propene oligomerization rates (503 K), interpreted using effectiveness factor formalisms, revealed the strong influence of intracrystalline diffusion limitations caused by the occlusion of heavier oligomer products within zeolitic micropores during reaction, consistent with prior reports. Transient changes in dimerization rates upon step changes in propene pressure revealed more severe diffusion limitations for Al-MFI@Si-MFI than Al-MFI materials possessing external acid sites, despite similar transient 2,3-dimethylbutane adsorption rates (298 K) on both core and core@shell materials indicating that additional diffusion resistances were not introduced inherently into core@shell materials via siliceous shell growth. Rather, passivation of external acid sites allows <em>in situ</em> formation of recalcitrant surface carbonaceous deposits during oligomerization catalysis, which caused irreversible deactivation with time-on-stream requiring regeneration under oxidative treatments. Overall, these findings provide kinetic and mechanistic insights into the role of external acid sites in zeolites to mitigate the formation of recalcitrant carbonaceous deposits during reaction, which introduce additional diffusional barriers that influence rates, product selectivity and deactivation of zeolites during alkene oligomerization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116107"},"PeriodicalIF":6.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723868","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 lytic polysaccharide monooxygenases (LPMOs) for immobilisation on carbon nanotubes","authors":"Kelsi R. Hall ,&nbsp;Carlotta Pontremoli ,&nbsp;Tom Z. Emrich-Mills ,&nbsp;Fabrizio Careddu ,&nbsp;Matteo Bonomo ,&nbsp;Claudia Barolo ,&nbsp;Vincent G.H. Eijsink ,&nbsp;Silvia Bordiga ,&nbsp;Morten Sørlie","doi":"10.1016/j.jcat.2025.116108","DOIUrl":"10.1016/j.jcat.2025.116108","url":null,"abstract":"<div><div>Lytic polysaccharide monooxygenases (LPMOs) are mononuclear copper-containing enzymes that are able to oxidise C–H bonds in the glycoside linkages of polysaccharides. However, LPMOs are prone to oxidative damage, particularly in the absence of an adequate substrate. In this work, we investigated whether we could immobilise LPMOs and whether such immobilisation could enhance the stability of LPMOs while preserving the essential catalytic properties of the copper active site. Two LPMOs from different families, <em>Ls</em>AA9A and <em>Sc</em>AA10C, were selected and immobilised on carboxylic acid functionalised multiwalled-CNTs, using a two-step carbodiimide activation reaction. To improve the frequency of enzyme immobilisation and guide site-specific orientation, the enzymes were engineered, introducing two lysine residues on two different loops on the LPMO surface. Assessment of the oxidase and peroxidase activities of the LPMO-MWCNT bioconjugates showed that immobilisation of the engineered LPMO was much more efficient compared to the wild-type enzymes. The immobilised enzymes still showed activity on several substrates, confirming retained catalytic competence following immobilisation. Incubation of the free and immobilised LPMOs under damaging conditions indicated a protective effect of immobilisation for <em>Ls</em>AA9A-MWCNT, indicating that, for some LPMOs, immobilisation on MWCNTs may protect against oxidative damage.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116108"},"PeriodicalIF":6.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723869","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":"Unveiling the pathways and site requirements of methanol oxidative dehydrogenation on MoO3/TiO2 catalysts: An operando-FTIR study","authors":"Gabriel Galdames ,&nbsp;Bastián Fuentes ,&nbsp;Daviel Gómez ,&nbsp;Patricia Concepción ,&nbsp;Romel Jiménez ,&nbsp;Alejandro Karelovic","doi":"10.1016/j.jcat.2025.116094","DOIUrl":"10.1016/j.jcat.2025.116094","url":null,"abstract":"<div><div>Methanol oxidative dehydrogenation was studied on sub-monolayer and crystalline MoO₃/TiO₂-supported catalysts using operando-FTIR spectroscopy. Results revealed two distinct methyl formate (MF) formation pathways, determined by the molybdenum oxide structure. Quantitative and qualitative evidence indicated that MF and dimethoxymethane (DMM) formation occur via distinct reaction intermediates. MF formation is linked to surface formate consumption, supported by the similarity between steady-state MF formation rate measured in a fixed-bed reactor and transient initial formate consumption rate determined by operando-FTIR. Apparent activation energies for HCOO* consumption (90 and 88 kJ mol⁻¹) and MF formation (83 and 51 kJ mol⁻¹) for 2.5 and 15 at. Mo nm⁻² samples, respectively, indicate that the formation pathway depends on the molybdenum oxide structure. Oligomeric, octahedral molybdenum oxide catalysts produce MF via adsorbed formate consumption, while crystalline MoO₃ catalysts enable a parallel pathway, likely involving hemiacetal intermediates. This change in reaction pathway correlates with the structural transition from oligomeric to crystalline molybdenum oxide, as characterized by XRD, in situ Raman spectroscopy, FTIR of low-temperature CO adsorption, and XPS, among other techniques. The increase of surface formate consumption is related to the enhancement of the redox properties of the catalyst, attributed to interactions of molybdenum oxide with titania support and the presence of readily reducible Mo⁶⁺ sites that influence adsorbed formaldehyde reaction pathways. The observed activity and selectivity are explained by a three-active-site mechanism: molybdenum oxide redox sites for methanol dehydrogenation, molybdenum oxide acid sites for hemiacetal and DMM formation, and molybdenum-titania interfacial sites for HCOO* and MF formation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116094"},"PeriodicalIF":6.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723938","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 facile strategy to prepare single-atom catalysts anchored on TiO2 with multiple oxygen vacancies for photocatalytic hydrogen evolution","authors":"Cailing Wu ,&nbsp;Mingming Sun ,&nbsp;Xinyang Gao ,&nbsp;Qifei Huang ,&nbsp;Zhaojun Min ,&nbsp;Yanxing Zhang ,&nbsp;Jianji Wang","doi":"10.1016/j.jcat.2025.116105","DOIUrl":"10.1016/j.jcat.2025.116105","url":null,"abstract":"<div><div>Single atom catalysts (SACs) supported on metal oxide are usually prepared at high temperature, high pressure, and complex process. Herein, a new strategy is developed to prepare SACs anchored on vacancy-rich TiO₂ using Ti₂O₃ as the support precursor under mild conditions, where Ti³⁺ on Ti₂O₃ surface acts as “traps” to capture and then reduce metal ions through electron transfer without using reducing agents. This approach is universally applicable for different single metal atoms supported on diverse phases of TiO₂ (anatase, rutile, metastable and mixed counterpart). The as-obtained Pt₁/TiO₂ with controllable Pt loading and multiple oxygen vacancies (Ov) exhibits excellent activity in photocatalytic H₂ evolution. At optimal conditions, the H₂ evolution rate is up to 95,180 μmol g⁻¹ h⁻¹, which is the highest for TiO₂ supported SACs reported.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116105"},"PeriodicalIF":6.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723937","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":"Zn modulating the metal support interaction to promote the sintering resistance of hydrotalcite-derived NiZnAl catalyst for methane cracking","authors":"Mengjie Cao ,&nbsp;Shuangde Li ,&nbsp;Shikun Wang ,&nbsp;Weichen Xu ,&nbsp;Xin Zhou ,&nbsp;Guangxin Ma ,&nbsp;Yunfa Chen","doi":"10.1016/j.jcat.2025.116103","DOIUrl":"10.1016/j.jcat.2025.116103","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116103"},"PeriodicalIF":6.5,"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 ,&nbsp;Jia Chen ,&nbsp;Jinxu Fang,&nbsp;Zhiwei Huang,&nbsp;Mingshuo Tian,&nbsp;Qiqi Zhou,&nbsp;Wen Chen,&nbsp;Juanjuan Gong,&nbsp;Junhong Chen,&nbsp;Shuangning Gan,&nbsp;Xinlong Liao,&nbsp;Xiaomin Wu,&nbsp;Huazhen Shen,&nbsp;Huawang Zhao,&nbsp;Guohua Jing","doi":"10.1016/j.jcat.2025.116100","DOIUrl":"10.1016/j.jcat.2025.116100","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116100"},"PeriodicalIF":6.5,"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,&nbsp;Ke Li,&nbsp;Wenjie Shi,&nbsp;Keren He,&nbsp;Han Xie","doi":"10.1016/j.jcat.2025.116106","DOIUrl":"10.1016/j.jcat.2025.116106","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116106"},"PeriodicalIF":6.5,"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 ,&nbsp;Xiaohui Liu ,&nbsp;Yong Guo ,&nbsp;Lin Dong ,&nbsp;Zupeng Chen ,&nbsp;Yanqin Wang","doi":"10.1016/j.jcat.2025.116085","DOIUrl":"10.1016/j.jcat.2025.116085","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116085"},"PeriodicalIF":6.5,"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":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}