Journal of Catalysis最新文献_第2页

Unraveling the active site for CO2 hydrogenation to methanol over Cu/ZnO catalysts: insights from DFT and microkinetic modeling Cu/ZnO催化剂上CO2加氢制甲醇活性位点的揭示：来自DFT和微动力学模型的见解

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-06 DOI: 10.1016/j.jcat.2025.116460

Yu Zhang , Pengfei Du , Jingyuan Mei , Xinxin Tian , Shuanglin Qu

{"title":"Unraveling the active site for CO2 hydrogenation to methanol over Cu/ZnO catalysts: insights from DFT and microkinetic modeling","authors":"Yu Zhang , Pengfei Du , Jingyuan Mei , Xinxin Tian , Shuanglin Qu","doi":"10.1016/j.jcat.2025.116460","DOIUrl":"10.1016/j.jcat.2025.116460","url":null,"abstract":"<div><div>Extensive efforts have been devoted to the Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> catalyst system, which is widely applied in the industrial methanol synthesis from CO<sub>2</sub>. However, the nature of active sites remains controversial due to challenges in experimentally isolating contributions from different surface structures and the absence of standardized theoretical comparisons. Here, we systematically study several representative active sites on Cu/ZnO catalysts using DFT calculations and microkinetic modeling. The Cu/ZnO interface exhibits the highest intrinsic activity, with a turnover frequency (TOF) of 1.4 × 10<sup>–2</sup> s<sup>−1</sup> under typical reaction conditions, which is over four times higher than that of the Cu–Zn alloys and consistent with experimental observations. In contrast, the ZnO/Cu(111) overlayer is inactive due to prohibitively high barriers along all pathways. Reaction pathway analysis indicates that methanol synthesis proceeds primarily via the HCOO pathway, rather than through direct CO<sub>2</sub> dissociation followed by CO hydrogenation. In addition, we find that a high H<sub>2</sub>O pressure in the system may further increase the surface coverage of OH* or O*, thereby hindering methanol formation by blocking active sites. These findings highlight the importance of considering adsorbate–adsorbate interactions in microkinetic modeling. Furthermore, tuning the coverage of specific intermediate species or the concentration of product can effectively enhance the reaction activity. This work offers theoretical insights into the fundamental origins of catalytic activity in Cu/ZnO systems and may facilitate the rational design of next-generation catalysts for methanol synthesis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116460"},"PeriodicalIF":6.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235311","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}

引用次数: 0

Strategies to improve the activity and stability of Fe-based catalysts for oxygen electrocatalysis 提高铁基氧电催化催化剂活性和稳定性的策略

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-06 DOI: 10.1016/j.jcat.2025.116462

Qiuyue Lu, Zhenlu Wang, Jingqi Guan

引用次数: 0

Synergistic acid–base interplays: Zeolite-catalyzed CH3Cl conversion to light olefins boosted by MgO-driven CH3Cl spillover 协同酸碱相互作用：沸石催化的CH3Cl转化为轻烯烃由mgo驱动的CH3Cl溢出

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-06 DOI: 10.1016/j.jcat.2025.116464

Seungdon Kwon , Jun Hyeok Heo , Changgi Kim, Woosung Leem, Hanbit Jang, Kyungsu Na

{"title":"Synergistic acid–base interplays: Zeolite-catalyzed CH3Cl conversion to light olefins boosted by MgO-driven CH3Cl spillover","authors":"Seungdon Kwon , Jun Hyeok Heo , Changgi Kim, Woosung Leem, Hanbit Jang, Kyungsu Na","doi":"10.1016/j.jcat.2025.116464","DOIUrl":"10.1016/j.jcat.2025.116464","url":null,"abstract":"<div><div>Chloromethane (CH<sub>3</sub>Cl), a reactive C<sub>1</sub> molecule, has been underexplored compared to traditional C<sub>1</sub> molecules like CO, CO<sub>2</sub>, CH<sub>4</sub>, and CH<sub>3</sub>OH that have long been at the center of C<sub>1</sub> chemistry. Herein, the catalytic chloromethane–to–olefin (CMTO) reaction was investigated with zeolite-based heterogeneous acid catalysts. H-ZSM-5 zeolites with controlled Si/Al ratios were investigated, revealing that CH<sub>3</sub>Cl conversion, catalyst lifetime, and light olefin (<span><math><mrow><msubsup><mi>C</mi><mrow><mn>2</mn><mo>-</mo><mn>4</mn></mrow><mo>=</mo></msubsup></mrow></math></span>) selectivity depended on zeolite acidity and MgO addition. While MgO alone enabled CH<sub>3</sub>Cl activation via Lewis acid–base interactions, its independent catalytic play pales compared to the superior performance of zeolites. However, balancing the zeolite acidity with MgO loading doubled or even tripled CH<sub>3</sub>Cl conversion compared to the independent performance of zeolites, achieving nearly 100 % CH<sub>3</sub>Cl conversion with 86.5 % <span><math><mrow><msubsup><mi>C</mi><mrow><mn>2</mn><mo>-</mo><mn>4</mn></mrow><mo>=</mo></msubsup></mrow></math></span> selectivity without deactivation. In-situ diffuse reflectance infrared Fourier transform spectroscopy showed that both zeolite acid sites and MgO activated CH<sub>3</sub>Cl simultaneously, during which MgO induced a CH<sub>3</sub>Cl spillover to the zeolite acidic site, resulting in the boosted CH<sub>3</sub>Cl conversion. This study establishes a new road to efficient and selective C<sub>1</sub> molecular conversion using CH<sub>3</sub>Cl boosted by CH<sub>3</sub>Cl spillover, which would be extended to methyl spillover-mediated catalytic conversion to various chemicals.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116464"},"PeriodicalIF":6.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235310","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}

引用次数: 0

Harnessing light to facilitate methanol conversion for high-efficiency hydrogen production under mild conditions 利用光促进甲醇转化，在温和条件下高效制氢

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-06 DOI: 10.1016/j.jcat.2025.116458

Weiwei Deng, Chenghao Yao, Beigang Zhao, Xiangqian He, Rui Lang, Lei Li, Zhan Lin

{"title":"Harnessing light to facilitate methanol conversion for high-efficiency hydrogen production under mild conditions","authors":"Weiwei Deng, Chenghao Yao, Beigang Zhao, Xiangqian He, Rui Lang, Lei Li, Zhan Lin","doi":"10.1016/j.jcat.2025.116458","DOIUrl":"10.1016/j.jcat.2025.116458","url":null,"abstract":"<div><div>For hydrogen storage applications, methanol serves as an ideal medium that effectively addresses storage and transportation challenges based on methanol steam reforming (MSR), which requires high temperatures (＞ 250 °C). Metal nanoparticles (e.g., Cu) with a localized surface plasmon resonance (LSPR) effect can utilize light to generate hot carriers for chemical reactions. Herein, the as-prepared Ga-doped CuZn catalyst (CuZn10Ga) achieves an exceptional H<sub>2</sub> production rate of 243.1 ± 4.7 mmol·g<sup>−1</sup>·h<sup>−1</sup> with near-perfect CO<sub>2</sub> selectivity (99.9 %) and negligible CO selectivity (0.1 %), while maintaining excellent stability over 150 h under mild conditions (190 °C, 500 mW·cm<sup>−2</sup>). Detailed experimental studies reveal that Ga induced strong metal-support interactions (SMSI) in the CuZn10Ga, creating a high density of Cu-ZnO<sub>x</sub> interfacial active sites. Under photo-thermal conditions (190 °C, 500 mW·cm<sup>−2</sup>), light enhances both methoxy (*OCH<sub>3</sub>) conversion and formate (*HCOO) decomposition efficiency, as verified by catalytic experiments and <em>in situ</em> DRIFTS. This work offers valuable insights into the precise design of noble-metal-free active sites and the development of low-temperature activation technologies.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116458"},"PeriodicalIF":6.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229394","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}

引用次数: 0

Tandem confinement of sub-nanometer Pt–Cu sites in USY zeolite enables high NH3-SCO selectivity across an ultra-wide temperature window 在USY沸石中，亚纳米级Pt-Cu位点的串联约束使NH3-SCO在超宽温度窗内具有高选择性

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-06 DOI: 10.1016/j.jcat.2025.116463

Yanfei Liu , Yanbo Pu , Chun Du , Jie Xu , Yaohui Dun , Chengxiong Wang , Yunkun Zhao , Jun Huang , Bin Shan , Rong Chen

{"title":"Tandem confinement of sub-nanometer Pt–Cu sites in USY zeolite enables high NH3-SCO selectivity across an ultra-wide temperature window","authors":"Yanfei Liu , Yanbo Pu , Chun Du , Jie Xu , Yaohui Dun , Chengxiong Wang , Yunkun Zhao , Jun Huang , Bin Shan , Rong Chen","doi":"10.1016/j.jcat.2025.116463","DOIUrl":"10.1016/j.jcat.2025.116463","url":null,"abstract":"<div><div>Selective catalytic oxidation of ammonia (NH<sub>3</sub>-SCO) to N<sub>2</sub> is crucial for abating residual NH<sub>3</sub> emissions, but existing catalysts struggle to combine low-temperature activity with high N<sub>2</sub> selectivity due to competitive Pt-NO interactions. Here we design a tandem confinement catalyst by depositing sub-nanometer Pt clusters (∼0.72 nm) inside the supercages of a Cu-exchanged USY zeolite via atomic layer deposition (ALD), creating intimately paired Pt–Cu active sites. This confined Pt/Cu-USY ALD catalyst achieves >90 % NH<sub>3</sub> conversion and >90 % N<sub>2</sub> selectivity across an exceptionally broad 170-300°C window under simulated exhaust conditions, surpassing all previously reported Pt-based NH<sub>3</sub>-SCO catalysts. The simultaneously enhanced low-temperature activity and high-temperature N<sub>2</sub> selectivity of the Pt/Cu-USY ALD catalyst can be attributed to the spatial confinement of Pt clusters within the Cu-USY framework, which leads to an expanded NO desorption window (150–350 °C). Detailed <em>in situ</em> studies further reveal that N<sub>2</sub>O<sub>4</sub> species preferentially serve as NO storage intermediates on the Pt/Cu-USY ALD catalyst surface at low temperatures, exhibiting significantly lower formation barriers compared to free nitrates, which dominate as intermediates in conventional Pt–Cu systems. This effectively mitigates free nitrate–induced site poisoning and overcomes the typical activity–selectivity trade-offs observed in conventional Pt–Cu dual-site catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116463"},"PeriodicalIF":6.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235418","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}

引用次数: 0

A melt-based reaction pathway for CO2 and CH4 conversion to syngas and carbon using liquid In–Sn 利用液态In-Sn将CO2和CH4转化为合成气和碳的熔融反应途径

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-05 DOI: 10.1016/j.jcat.2025.116465

Genpei Cai , Nikil Surya RajaPrabu , Juhi Srivastava , Korbinian Lechner , Jorit Körber , Zhiyuan Zong , Kevin J. Smith , Vishal Agarwal , D. Chester Upham

{"title":"A melt-based reaction pathway for CO2 and CH4 conversion to syngas and carbon using liquid In–Sn","authors":"Genpei Cai , Nikil Surya RajaPrabu , Juhi Srivastava , Korbinian Lechner , Jorit Körber , Zhiyuan Zong , Kevin J. Smith , Vishal Agarwal , D. Chester Upham","doi":"10.1016/j.jcat.2025.116465","DOIUrl":"10.1016/j.jcat.2025.116465","url":null,"abstract":"<div><div>Molten In–Sn has been recently reported as an effective catalyst for directly producing 2:1 H<sub>2</sub>:CO syngas and solid carbon from CO<sub>2</sub> and CH<sub>4</sub> in a single reaction, equivalent to the combined reactions of methane pyrolysis and dry reforming. In the present work, when reactants are alternately fed, mass balances indicate that CO<sub>2</sub> reacts to form an [O] species that oxidizes CH<sub>4</sub>. Also, CH<sub>4</sub> is converted to a [C] species that reduces CO<sub>2</sub>. The presence of accumulated [O] did not significantly affect the experimentally determined activation energies of 229 kJ/mol vs. 222 kJ/mol. We performed ab initio molecular dynamics (AIMD) simulations and density functional theory (DFT) calculations, to probe the dynamic structural evolution and to obtain atomistic insights into the behavior of the molten In–Sn alloy at the molecular level. This integrated approach also facilitated the evaluation of activation energy barriers associated with key reaction pathways. Simulations indicate that [O] are solvated; rapidly switching neighbors between Sn and In, which is unique to a molten catalyst. The presence of accumulated [C] significantly decreased the experimentally observed apparent CO<sub>2</sub> activation energy from 154 kJ/mol to 75 kJ/mol, which is lower than the direct reaction between CO<sub>2</sub> and solid graphite. This finding supports the simulations that indicate [C] formed in the melt is solvated, chemically distinct from solid carbon, and can play a critical role in enhancing catalytic performance. Large fluctuations in adsorbate binding energies were theoretically observed over time, suggesting the creation of transient sites that are fleetingly active, and facilitate the formation of solvated [O] and [C] intermediates unique to a molten catalyst surface.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116465"},"PeriodicalIF":6.5,"publicationDate":"2025-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229395","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}

引用次数: 0

Selective conversion of glycerol to potassium lactate and hydrogen gas in water catalyzed by a ruthenium complex bearing a functional ligand [(p-cymene)Ru(2-OH-6-BzlmHpy)Cl][Cl] 钌配合物催化甘油在水中选择性转化为乳酸钾和氢气[（对伞花烃）Ru(2-OH-6-BzlmHpy)Cl][Cl]

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-03 DOI: 10.1016/j.jcat.2025.116442

Beixuan Dong, Yuexin Ji, Feifei Zhou, Nguyen Thanh Tung, Yuran Fan, Feng Li

引用次数: 0

Cobalt-driven selective hydrogermylation of terminal and internal alkynes 末端和内炔的钴驱动选择性加氢化反应

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-02 DOI: 10.1016/j.jcat.2025.116467

Konstancja Broniarz, Dariusz Lewandowski, Grzegorz Hreczycho

引用次数: 0

Aqueous-phase photocatalytic performance of defective carbon nitride: the discrepancy between density functional theory calculations predicting and practical results 缺陷氮化碳水相光催化性能：密度泛函理论计算预测与实际结果的差异

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-02 DOI: 10.1016/j.jcat.2025.116466

Haoxiang Zhong , Cheng Yang , Chuang Li , Shangfeng Tang , Meifang Li , Xi Hu , Haiyin Xu , Jian Ye , Xinjiang Hu , Jiaqin Deng , Hui Wang

{"title":"Aqueous-phase photocatalytic performance of defective carbon nitride: the discrepancy between density functional theory calculations predicting and practical results","authors":"Haoxiang Zhong , Cheng Yang , Chuang Li , Shangfeng Tang , Meifang Li , Xi Hu , Haiyin Xu , Jian Ye , Xinjiang Hu , Jiaqin Deng , Hui Wang","doi":"10.1016/j.jcat.2025.116466","DOIUrl":"10.1016/j.jcat.2025.116466","url":null,"abstract":"<div><div>Density Functional Theory (DFT) calculation is a powerful tool for inverse design photocatalysts. However, calculated predictions need to be trusted and expected by experimental researchers. Herein, we have selected graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) as a representative and constructed atomic-level defects to create theoretical and practical performance discrepancies for comparison and discussion. We predicted the theoretical properties of carbon nitride with different defects by DFT calculations, then tried to synthesize these samples in the experiments, and tested the practical properties of different samples by characterization and two classical aqueous-phase photocatalytic experimental systems (photocatalytic organics degradation and photocatalytic hydrogen peroxide production). The results showed that the theoretical predictions of photocatalysts reach an impressive approximation to the practical performance, especially in the simulation of photoelectric properties and the calculation of intermediate adsorption capacity. This groundbreaking work opens new avenues for photocatalyst prediction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116466"},"PeriodicalIF":6.5,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209611","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}

引用次数: 0

Rapid and regioselective synthesis of mono-, di- and multi-cyanofunctionalized (poly)siloxanes via Ni-catalyzed hydrocyanation of vinyl(poly)siloxanes 镍催化乙烯基（聚）硅氧烷氢氰化反应，快速、区域选择性地合成单、二和多氰化聚硅氧烷

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-09-28 DOI: 10.1016/j.jcat.2025.116457

Jiawen Hu, Pengyong Fang, Mingdong Jiao, Jinguo Long, Xianjie Fang

引用次数: 0