Journal of Catalysis最新文献

{"title":"High selectivity and efficiency in 5-hydroxymethylfurfural oxidation: synergistic oxygen activation by Co-Nx sites on nitrogen-doped carbon supported single-atom cobalt","authors":"Shutian Lin ,&nbsp;Zijian Liu ,&nbsp;Yaocheng Xie ,&nbsp;Yuanhong Zhong ,&nbsp;Ming Sun ,&nbsp;Lin Yu","doi":"10.1016/j.jcat.2025.116337","DOIUrl":"10.1016/j.jcat.2025.116337","url":null,"abstract":"<div><div>2,5-Furandicarboxylic acid (FDCA), a pivotal polymer industry chemical, is primarily synthesized via the oxidation of 5-hydroxymethylfurfural (HMF). Non-precious metal catalysts exhibit significant potential in this process, yet harsh conditions and inefficient atom utilization hinder their broader use. Herein, a Co-based catalyst (Co_1.3-N-C) with highly dispersed Co single atoms, derived from zeolitic imidazolate frameworks (ZIFs), was successfully synthesized. It activates the adsorbed O₂ into both radicals and non-radicals with high catalytic efficacy through well-defined active sites (Co-N₄). The catalyst achieved a complete conversion of HMF to FDCA within one hour at 90 °C under 0.1 MPa O₂, with a yield of 99.6% and an impressive FDCA formation rate of 52.34 μmol min⁻¹ g⁻¹. This performance is comparable to the activity of many reported precious and non-precious metal catalysts. The catalytic mechanism, along with the roles of distinct reactive species, superoxide radical (O₂^<img>−) and singlet oxygen (¹O₂), at various stages of the selective oxidation of HMF to FDCA, was elucidated through theoretical calculations. The results highlight the excellent activity and high selectivity of Co_1.3-N-C, which is promising for the sustainable production of bio-based chemicals and materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116337"},"PeriodicalIF":6.5,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712442","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":"Modulating surface charge and offering hydrogen bonding for copper-based materials toward efficient electrocatalytic CO2 to ethylene","authors":"Zhen Liu ,&nbsp;Xiao-Yun Li ,&nbsp;Xiao-Yu Yang ,&nbsp;Zhan Liu ,&nbsp;Yu Li ,&nbsp;Yi-Yong Huang ,&nbsp;Zhao Deng ,&nbsp;Shen Yu ,&nbsp;Ming-Hui Sun ,&nbsp;Li-Hua Chen ,&nbsp;Bao-Lian Su ,&nbsp;Yi-Long Wang","doi":"10.1016/j.jcat.2025.116336","DOIUrl":"10.1016/j.jcat.2025.116336","url":null,"abstract":"<div><div>Cuprous oxide (Cu₂O) has been regarded as a highly promising category of electrocatalyst for carbon dioxide reduction reaction (CO₂RR). Nevertheless, the development of highly efficient Cu-based electrocatalysts for the CO₂-to-ethylene conversion as well as the elucidation of the possible catalytic mechanism, remain challenging areas of research. This is due to the fact that the electrocatalytic CO₂RR conversion to ethylene (C₂H₄) is a process comprising numerous steps and a sophisticated electrocatalytic mechanism. The absence of a comprehensive understanding of the reaction process is likely to impose significant limitations on the design of highly efficient Cu-based electrocatalysts. In this work, the nitrogen-doped Cu₂O nanocubes modified with dodecylamine have been synthesized <em>via</em> a facile refluxing strategy to efficiently promote the conversion of CO₂ to C₂H₄. The present work focuses on a comprehensive analysis of the underlying mechanisms that underpin the enhanced CO₂RR activity of the as-synthesized electrocatalysts. First, the introduction nitrogen atoms into electrocatalysts can efficiently modulate the charge of Cu sites, which favors the adsorption of the *CO intermediate. Additionally, the presence of hydrogen bonding serves to stabilize the *CHO intermediate and weaken the C<img>O bond of the O*CCHO intermediate, thereby facilitating the hydrogenation process to the O*CCHOH intermediate. Last but not least, our electrocatalyst present a significant advantage over both the dodecylamine-modified electrocatalyst and the electrocatalyst that has not undergone N doping and dodecylamine in the dehydroxylation of OH*CHCH₂ to *CHCH₂ intermediates. This is due to the configuration transformation of the *CHCH₂ intermediate, which favors the formation of C₂H₄. Our work proposes a feasible strategy for modulating charge coupled to offering hydrogen bonding for the design and synthesis of the Cu-based electrocatalysts, with the objective of achieving efficient conversion of CO₂ to C₂H₄.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116336"},"PeriodicalIF":6.5,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701834","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":"Acid-base pairs of acidic ionic liquids-functionalized covalent triazine frameworks with controllable morphology for boosting C–O bond cleavage of carbohydrate","authors":"Xiaofei Liu,&nbsp;Daiyu Song,&nbsp;Yunyun Liu,&nbsp;Zhao Huang,&nbsp;Xinyao Wang,&nbsp;Kezhi Wang,&nbsp;Yuxin Yang,&nbsp;Yihang Guo","doi":"10.1016/j.jcat.2025.116335","DOIUrl":"10.1016/j.jcat.2025.116335","url":null,"abstract":"<div><div>The cleavage of C–O bonds in biomass-derived carbohydrates is of great significance for the conversion of biomass to chemicals and fuels. We demonstrated that various F127-directed covalent triazine frameworks functionalized by sulfonic acid-based ionic liquids ([C₃N][OTf]-FCTF) were synthesized by a two-step synthesis process. The interesting morphology of spherical nanofiber of the [C₃N][OTf]-FCTF(0.25)-10 catalyst was obtained by carefully adjusting the usage of both F127 and ethanol in the synthetic system. The 5-hydroxymethylfurfural synthesis reaction parameters of were first optimized using the [C₃N][OTf]-FCTF(0.25)-10 <em>via</em> response surface methodology. The [C₃N][OTf]-FCTF(0.25)-10 exhibited high catalytic activity, and outperformed other CTF-based catalysts with different morphologies and commercial solid acids in the conversion of carbohydrates (e.g., fructose, inulin, sucrose and honey). This is due to the advantages of the loose spherical nanofiber, the rich N-containing units, the suitable Brønsted acid nature and the adjacent acid-base pairs on the surface of the catalyst. The high Brønsted acidity of [C₃N][OTf]-FCTF(0.25)-10 played a positive role in the selective synthesis of levulinic acid from carbohydrates. The theoretical calculations demonstrated that discrepancies in electron cloud distribution between constructed acid-base pairs and N-rich groups in the catalyst could facilitate the cleavage of C–O bonds in fructose molecules. The Fukui function combined with experimental results elucidated the reaction pathways. The robust interaction between –[C₃N][OTf] groups and frameworks ensured the excellent reusability of [C₃N][OTf]-FCTF catalysts. This study will provide a novel approach for synthesizing CTF-based solid acids with controllable morphology, enabling the high-value utilization of carbohydrates.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116335"},"PeriodicalIF":6.5,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144710829","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":"Caffeine carbon supported reusable cobalt catalyzed reductive amino formylation of carbonyl compound using ammonium formate","authors":"Sadhan Dey ,&nbsp;Seema D. Thakur ,&nbsp;Trishit Roy ,&nbsp;Anirban Sau ,&nbsp;Ratan Debnath ,&nbsp;Rajaram Bal ,&nbsp;Sabuj Kundu","doi":"10.1016/j.jcat.2025.116334","DOIUrl":"10.1016/j.jcat.2025.116334","url":null,"abstract":"<div><div>Reductive amino formylation (RAF) of carbonyl compounds employing ammonium formate faces major obstacles due to selectivity issues. Utilizing biowaste-derived caffeine carbon, the development of sustainable catalytic systems for diverse organic transformations is an exciting area of research. In this outlook, we have established a caffeine carbon-supported reusable cobalt-based catalytic system for the selective synthesis of <em>N</em>-formylated products via RAF of a variety of carbonyl compounds using ammonium formate as an N1, C1, and hydrogen source. Herein, we have developed an efficient catalytic system by fine-tuning the Co-Nx and nitrogen content for effective utilization of ammonium formate towards RAF of carbonyl compounds. The practical application of this methodology was demonstrated through gram-scale synthesis and RAF of acetophenone derivatives containing biologically relevant motifs. Various kinetic and control experiments were performed to understand the catalytic process. The catalyst was recycled up to the 7^th time without significant loss of catalytic activity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116334"},"PeriodicalIF":6.5,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701835","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":"Indium-powered boost: Enhancing the photocatalytic efficiency of π-expanded pyrazinoporphyrins in sulfide oxidation","authors":"Ekaterina S. Shremzer ,&nbsp;Daria A. Polivanovskaia ,&nbsp;Kirill P. Birin ,&nbsp;Aslan Yu. Tsivadze","doi":"10.1016/j.jcat.2025.116327","DOIUrl":"10.1016/j.jcat.2025.116327","url":null,"abstract":"<div><div>A crucial enhancement of photocatalytic performance of a series of novel π-expanded indium(III) porphyrins bearing annelated pyrazine heterocycle substituted by or fused with various peripheral fragments, namely ethyl, 4-methylphenyl, phenanthrene, phenanthroline, and acenaphthene, has been revealed and investigated in detail. The introduction of In(III) ion into the porphyrin cavity resulted in significant increase in both the photostability and photocatalytic activity of the porphyrin-based photosensitizers. The synthesized In(III) pyrazinoporphyrins demonstrated exceptional conversion rates across a representative set of substrates in selective photocatalytic oxidation of organic sulfides to the corresponding sulfoxides. The study also underscored the crucial role of solvent selection in optimization of photocatalytic oxidation of sulfides. Notably, the phenanthrene-appended In(III) pyrazinoporphyrinate exhibited outstanding photocatalytic efficiency even at extremely low loading, achieving an exceptionally high TOF of 309 000 h⁻¹ in oxidation of dibutyl sulfide. Furthermore, gram-scale photooxidation of sulfides showed remarkable catalytic efficiency and scalability under mild conditions in the presence of «green» solvents.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116327"},"PeriodicalIF":6.5,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684941","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":"Enhanced built-in electric field facilitates charge separation and transfer in conjugated microporous polymers for photocatalytic CH trifluoromethylation of heterocycles","authors":"Tianyu Long ,&nbsp;Yong Zheng ,&nbsp;Tao Gao ,&nbsp;Han-Han Kong ,&nbsp;Qing-Qing Yang ,&nbsp;Wenli Xu ,&nbsp;Shangbin Xiao ,&nbsp;Liqun Ye ,&nbsp;Long Wang","doi":"10.1016/j.jcat.2025.116329","DOIUrl":"10.1016/j.jcat.2025.116329","url":null,"abstract":"<div><div>The limited carrier separation efficiency in conjugated microporous polymers (CMPs) remains a critical constraint for their photocatalytic performance. Recognizing the built-in electric field (BEF) as a crucial kinetic factor for promoting photoinduced carrier separation and migration, we developed a BEF intensification strategy through asymmetric extension of monomer conjugation systems. A series of CMPs were rationally designed and synthesized via metal-free Chichibabin reactions, featuring systematically varied π-conjugated architectures. Combined experimental and theoretical investigations demonstrate that asymmetric expansion of monomer π-conjugation effectively enhances the BEF intensity through optimized molecular polarization, thereby promoting directional charge separation and transport. This BEF enhancement enables efficient photocatalytic C<img>H trifluoromethylation of diverse bioactive heterocyclic compounds under visible light irradiation, achieving exceptional catalytic yields up to 98 %. Our findings establish fundamental correlations between asymmetric conjugation engineering and the BEF optimization, providing valuable insights for molecular-level design of high-performance polymeric photocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116329"},"PeriodicalIF":6.5,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684997","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 distinct effects between NiSn alloy and SnO sites in Ni-Sn bimetallic catalysts for selective hydrodeoxygenation of furfural to 2-methylfuran","authors":"Hao Zhao ,&nbsp;Xiaoqing Liao ,&nbsp;Haishuai Cui ,&nbsp;Wantong Liu ,&nbsp;Hean Luo ,&nbsp;Yang Lv ,&nbsp;Pingle Liu","doi":"10.1016/j.jcat.2025.116333","DOIUrl":"10.1016/j.jcat.2025.116333","url":null,"abstract":"<div><div>The selective hydrodeoxygenation of furfural (FFR) to 2-methylfuran (2-MF) is crucial for the high-value utilization of biomass resources. In this study, a series of Ni_nSn₁/MoO_x (n = 1, 2, 3, 4, 5) catalysts with varying metal ratios were synthesized <em>via</em> a glycine-assisted auto-ignition method and evaluated for FFR hydrodeoxygenation to 2-MF. The results reveal that an optimal Sn loading enhances the Ni-Sn interaction, promoting the formation of Ni-Sn alloys and improving the dispersion of metal nanoparticles. More importantly, the appropriate Sn addition facilitates the generation of SnO species, which serve as Lewis acid sites and accelerate the hydrodeoxygenation of the intermediate furfuryl alcohol (FA) to 2-MF. <em>In-situ</em> DRIFTS analysis demonstrates that Sn incorporation strengthens the adsorption of the C<img>O group in FFR and the C<img>OH group in FA, thereby enhancing 2-MF formation. Density functional theory (DFT) calculations further indicate that the Ni₄Sn₁ (111) crystal surface exhibits the lowest <em>d</em>-band center and the strongest electronic effect. Consequently, this surface shows the highest adsorption energies for H₂, FFR, and FA, the lowest adsorption energies for H* and 2-MF, and the smallest energy barrier for the conversion of FA to 2-MF. As a result, the Ni₄Sn₁/MoO_x catalyst achieves exceptional performance, delivering a 99.8 % yield of 2-MF at 170 °C. This work provides a novel strategy for designing efficient non-noble metal catalysts for the selective conversion of biomass-derived furfural to 2-MF.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116333"},"PeriodicalIF":6.5,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678207","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":"Resolving the Impacts of Sn Addition During CO Methanation Over PtxSny/γ-Al2O3","authors":"Robson L. Schuarca,&nbsp;Jesse Q. Bond","doi":"10.1016/j.jcat.2025.116332","DOIUrl":"10.1016/j.jcat.2025.116332","url":null,"abstract":"<div><div>Alloys are useful in catalysis practice. Adding a secondary metal, like Sn, to a noble metal, like Pt, can improve reactor-scale performance (conversion, selectivity, and stability), and we usually cite “alloy formation” as the underlying cause. Despite this, one rarely sees rigorous, experimental evidence that alloy formation actually leads to improved turnover frequencies. This is not to say that such rate enhancements are implausible. Alloy surfaces have geometric and electronic structures that are distinct from their monometallic analogs, so it stands to reason that they would have distinct intrinsic activities. Unfortunately, it is difficult to control the composition and structure of alloy surfaces under working conditions, which makes it difficult to define turnover frequencies and thus demonstrate enhanced intrinsic activity. We attempt to resolve these issues for CO methanation over Pt_xSn_y/γ-Al₂O₃. We consider the impacts of variations in metal composition and structure, and we establish a reasonable definition of turnover frequency to permit a comparison of monometallic and bimetallic samples. Variations in turnover rate are viewed alongside spectroscopic data to resolve the influences of electronic and geometric effects on methanation activity. The primary kinetic consequence of Sn addition in this system is disruption of extended Pt surfaces, which leads to a loss of Pt-Pt site pairs and a decrease in methanation turnover frequencies for Sn-rich alloys and intermetallic phases. We see no evidence that alloy formation alters the electronic interactions of CO and active sites that are quantifiably participating in CO methanation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116332"},"PeriodicalIF":6.5,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678214","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":"Preparation and optimization of dendritic Ni/Y-silica composite catalysts for naphthalene hydrocracking to BTX","authors":"Xiaoyang Kong,&nbsp;Zhentao Liu,&nbsp;Yutong Zou,&nbsp;Chunya Wang,&nbsp;Chunming Xu,&nbsp;Xilong Wang","doi":"10.1016/j.jcat.2025.116331","DOIUrl":"10.1016/j.jcat.2025.116331","url":null,"abstract":"<div><div>A novel hierarchical composite material (YD) is engineered via nano-assembly of Y microcrystals and dendritic mesoporous silica nanospheres (DMSNs), serving as superior supports for highly selective naphthalene hydrocracking catalysts (Ni/YD). The three-dimensional center-radial pore architecture of DMSNs shortens molecular diffusion paths and enhances the accessibility of catalytic active sites. Controlled incorporation of Y nanocrystals enriches acidic sites and optimizes metal-support interaction. Moreover, [Ni(en)₃](NO₃)₂ is used as the nickel precursor further improves metal dispersion, maximizing hydrogenation sites. Consequently, the optimized Ni/YD achieves 93.4 % naphthalene conversion with &gt;65 % BTX yield, exhibiting superior kinetics (reaction rate constant of 1.9 h⁻¹ and turnover frequency of 33.7 h⁻¹). Based on the proposed reaction pathway, appropriate acidity, open dendritic pores and highly dispersed Ni species synergistically promote the isomerization-cracking route selectivity and directed hydrocracking of naphthalene.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116331"},"PeriodicalIF":6.5,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678208","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 “Identification and evolution of active sites in isomorphously substituted Fe-ZSM-5 catalysts for methane dehydroaromatization (MDA)”. [J. Catl. 446 (2025) 116090/[YJCAT_116090]","authors":"Xinrui Zhang, Jordy Ramos-Yataco, Shan Jiang, Qingheng Lai, Selim Alayoglu, Jeffrey T. Miller, Tobin J. Marks, Justin M. Notestein","doi":"10.1016/j.jcat.2025.116322","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116322","url":null,"abstract":"No Abstract","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"9 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664600","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}