Applied Catalysis A: General最新文献_第8页

Promoted NOₓ adsorption under wet conditions: Mechanistic insights into Pd redispersion in hydrothermally aged Pd/CHA 湿条件下促进NOₓ吸附：水热老化Pd/CHA中Pd再分散的机理

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-09-03 DOI: 10.1016/j.apcata.2025.120539

Takeshi Ohtsu , Nao Tsunoji , Akira Oda , Atsushi Satsuma

{"title":"Promoted NOₓ adsorption under wet conditions: Mechanistic insights into Pd redispersion in hydrothermally aged Pd/CHA","authors":"Takeshi Ohtsu , Nao Tsunoji , Akira Oda , Atsushi Satsuma","doi":"10.1016/j.apcata.2025.120539","DOIUrl":"10.1016/j.apcata.2025.120539","url":null,"abstract":"<div><div>Passive NO<sub>x</sub> adsorbers (PNA) have been developed to adsorb NO<sub>x</sub> from low-temperature (less than 200°C) diesel exhaust streams containing water vapor. When H<sub>2</sub>O is present during NO<sub>x</sub> adsorption, H<sub>2</sub>O adsorbs on PNA, and this inhibits NO<sub>x</sub> adsorption. However, this study shows H<sub>2</sub>O-assisted NO<sub>x</sub> adsorption on Pd/CHA. This phenomenon was observed in Pd/CHA that had been hydrothermally aged at 600℃ and 750℃. Also, the H<sub>2</sub>O-assisted mechanism results from the co-adsorption of NO and H<sub>2</sub>O under wet conditions. In situ FT-IR spectroscopy and FT-EXAFS analysis reveal that hydration of Pd cations enhances NO<sub>x</sub> adsorption under wet conditions and induces redispersion of Pd cations from PdO<sub>x</sub>. This phenomenon increases the number of Pd cations, which are NO<sub>x</sub> adsorption sites, thereby increasing NO<sub>x</sub> adsorption. These findings establish a new design of PNA catalysts applicable to H<sub>2</sub>O-rich exhaust gases.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120539"},"PeriodicalIF":4.8,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Enhancing chemoselectivity via strong metal-support interaction: Selective hydrogenation of 4-chloronitrobenzene over Pd/TiO2 catalysts 通过强金属-载体相互作用增强化学选择性：Pd/TiO2催化剂上4-氯硝基苯的选择性加氢

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-09-03 DOI: 10.1016/j.apcata.2025.120540

Hiromu Akiyama , Koki Saegusa , Hiroshi Sampei , Takuma Higo , Kyogo Maeda , Toshiyuki Watanabe , Shigeru Kado , Hiromi Nakai , Yasushi Sekine

{"title":"Enhancing chemoselectivity via strong metal-support interaction: Selective hydrogenation of 4-chloronitrobenzene over Pd/TiO2 catalysts","authors":"Hiromu Akiyama , Koki Saegusa , Hiroshi Sampei , Takuma Higo , Kyogo Maeda , Toshiyuki Watanabe , Shigeru Kado , Hiromi Nakai , Yasushi Sekine","doi":"10.1016/j.apcata.2025.120540","DOIUrl":"10.1016/j.apcata.2025.120540","url":null,"abstract":"<div><div>Supported metal catalysts play an important role in various chemical reactions, including hydrogenation and dehydrogenation. Their activity and selectivity depend on factors such as the metal particle size and surface area and interaction between the metal and the support. Among these factors, “strong metal-support interaction” (SMSI) is a phenomenon by which metal particles supported on an oxide support are embedded under high-temperature reduction conditions, causing important changes in their surface adsorption properties and electronic states. Such electronic state changes reportedly alter the <em>d</em>-band centers of the metal and the adsorption energy of intermediates, thereby strongly influencing catalytic performance. For this study, we investigated SMSI effects on the selective hydrogenation of 4-chloronitrobenzene (4-ClNB) to 4-chloroaniline (4-ClAN) using a Pd/TiO<sub>2</sub> catalyst. This reaction requires reduction of the -NO<sub>2</sub> group while preventing dissociation of the -Cl group. Actually, Pd catalysts are known to have high reducing activity toward the -NO<sub>2</sub> group, but they also cause undesirable C-Cl bond dissociation, which reduces their selectivity. By contrast, we found that controlling the electronic state of Pd <em>via</em> SMSI can enhance the selectivity to 4-ClAN. The underlying mechanisms were elucidated using TPR, TEM, CO adsorption, DRIFTS, XAFS, XPS, and DFT calculation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120540"},"PeriodicalIF":4.8,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 catalytic cracking of LDPE to C2-C4 olefins over interconnected NZ@Al-meso-SiO2: Role of hierarchical porosity and acidity 串联催化裂化LDPE到C2-C4烯烃在互联NZ@Al-meso-SiO2：分级孔隙度和酸度的作用

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-09-02 DOI: 10.1016/j.apcata.2025.120538

Yutao Diao , Yali Zhang , Weikun Zhang , Yilin Cui , Wenqi Liu , Jingyan Zhang , Zhongfu Li , Conghua Liu

{"title":"Tandem catalytic cracking of LDPE to C2-C4 olefins over interconnected NZ@Al-meso-SiO2: Role of hierarchical porosity and acidity","authors":"Yutao Diao , Yali Zhang , Weikun Zhang , Yilin Cui , Wenqi Liu , Jingyan Zhang , Zhongfu Li , Conghua Liu","doi":"10.1016/j.apcata.2025.120538","DOIUrl":"10.1016/j.apcata.2025.120538","url":null,"abstract":"<div><div>Catalytic upcycling offers a promising route to valorize end-of-life polyolefins as high-value chemicals, yet significant challenges remain. Adjusting the hierarchical porosity and acidity of composites can effectively enhance polyolefins cracking efficiency. Thus, systematically studying their effects on cracking performance is essential. In the presented work, the interconnected NZ@Al-meso-SiO<sub>2</sub> composites are synthesized for the efficient tandem catalytic cracking of low-density polyethylene (LDPE) into light olefins (C<sub>2</sub>-C<sub>4</sub>). By adjusting the ZSM-5/meso-SiO<sub>2</sub> mass ratio and the Si/Al atomic ratio, the impact of hierarchical porosity and acidity on product distribution was systematically investigated. The results indicated that medium ZSM-5/meso-SiO<sub>2</sub> mass ratio (n = 0.3) facilitates the tandem cracking of LDPE and enhances mass transfer. The Al-meso-SiO<sub>2</sub> component selectively pre-cracks LDPE into intermediates and subsequently timely diffusion and deep cracking of the intermediates in nanosized ZSM-5, ultimately converting into C<sub>2</sub>-C<sub>4</sub> olefins. The low Si/Al ratio (50) demonstrates a high acid density and the Brønsted/Lewis (B/L) acid ratio, exhibits greater selectivity for light olefins compared to a higher Si/Al ratio. The optimized NZ@Al-meso-SiO<sub>2</sub>-0.3–50 delivers an impressive performance, achieving ∼50 wt% light olefin yields at 550 °C within just 15 min. This exceptional activity and selectivity significantly surpass conventional single-component catalysts, physical mixtures, as well as exceeding results reported in the literature. This rational design of synergistic tandem catalysts provides a powerful foundation for developing advanced composite materials for diverse catalytic upcycling and reaction processes.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120538"},"PeriodicalIF":4.8,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Moisture-enhanced CO2 desorption from alkali and alkaline earth metal-based sorbents direct air capture 从碱和碱土金属为基础的吸附剂的水分增强CO2解吸直接空气捕获

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-31 DOI: 10.1016/j.apcata.2025.120535

Soosan Kim, Xiao Lin, Hanqi Yang, Robert J. Farrauto

引用次数: 0

Enhancing H2 activation over Pt-WOx/SiO2 via IrO2 interface engineering for selective glycerol hydrogenolysis 通过IrO2界面工程提高Pt-WOx/SiO2上的H2活化选择性甘油氢解

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-31 DOI: 10.1016/j.apcata.2025.120533

Zhikun Zhao , Zheng Zhou , Yueqiang Cao , Jinghong Zhou , Xinggui Zhou

{"title":"Enhancing H2 activation over Pt-WOx/SiO2 via IrO2 interface engineering for selective glycerol hydrogenolysis","authors":"Zhikun Zhao , Zheng Zhou , Yueqiang Cao , Jinghong Zhou , Xinggui Zhou","doi":"10.1016/j.apcata.2025.120533","DOIUrl":"10.1016/j.apcata.2025.120533","url":null,"abstract":"<div><div>Catalytic hydrodeoxygenation of oxygenated compounds is of great importance to the sustainable production of biofuels and fine chemicals. Pt-based bifunctional catalysts exhibit excellent performance owing to their high efficiency in H<sub>2</sub> activation and subsequent hydrogen spillover, which enables them widely applied in biomass-derived oxygenate conversion. However, given the high cost of Pt, enhancing the hydrogenation activity of individual Pt sites is essential for improving overall catalytic efficiency and maximizing noble metal utilization. Herein, we report an IrO<sub>2</sub>-modification strategy to enhance hydrogen activation over Pt-WO<sub>x</sub>/SiO<sub>2</sub> catalysts for selective hydrogenolysis of glycerol. Structural characterizations reveal Ir incorporation induces the formation of Pt-O-Ir interface, which in turn promotes the generation of electron-deficient Pt<sup>δ+</sup> species. Diffuse reflection infrared Fourier transformed spectra of H<sub>2</sub> adsorption and Density functional theory calculations reveal that these Pt<sup>δ+</sup> sites promote hydrogen activation by significantly lowering the activation barrier for H<sub>2</sub> dissociation at the Pt-O-Ir interface. Catalytic performance tests confirm that the addition of 0.05 wt% Ir enhances the glycerol hydrogenolysis rate by 1.4-fold, while maintaining high selectivity toward 1,3-propanediol (56.1 %) at a glycerol conversion of 50.1 %. However, excessive Ir loading leads to partial coverage of Pt sites, reducing the number of accessible active centers and thus suppressing catalytic activity.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120533"},"PeriodicalIF":4.8,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Steam reforming of methanol over Li-doped Pt/m-ZrO2 掺锂Pt/m-ZrO2上甲醇的蒸汽重整

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-31 DOI: 10.1016/j.apcata.2025.120532

Denzel Megafu , Michela Martinelli , Dali Qian , Yağmur Hocaoğlu , Gary Jacobs

{"title":"Steam reforming of methanol over Li-doped Pt/m-ZrO2","authors":"Denzel Megafu , Michela Martinelli , Dali Qian , Yağmur Hocaoğlu , Gary Jacobs","doi":"10.1016/j.apcata.2025.120532","DOIUrl":"10.1016/j.apcata.2025.120532","url":null,"abstract":"<div><div>The effect of Li loading on 2 %Pt/m-ZrO<sub>2</sub> catalyst was explored using temperature programmed, chemisorption, microscopic, spectroscopic, and micro-reactor testing methods. Up to 0.54 %Li loading, despite a small decrease in methanol conversion, the selectivity was altered remarkably from favoring unselective H<sub>2</sub>-production pathways involving decarbonylation (300°C: 68.2 % CO, 30.3 % CO<sub>2</sub>) to favoring the selective H<sub>2</sub>-production pathway involving decarboxylation/dehydrogenation (300°C: 14.5 % CO, 85.2 % CO<sub>2</sub>). In addition, the methanation selectivity decreased from 1.5 % to just 0.3 %. The primary advantage of Li over Na and K promoters, previously studied, is that Li provides the remarkable boost in selectivity without a significant loss in activity. At optimum loadings for selectivity, there was only a 13 % drop in conversion by adding 0.54 wt%Li, while more severe drops of 40 % and 55 % occurred for 2.5 wt% Na and 3.06 wt% K (atomic loadings close, 325 °C). CO<sub>2</sub>-temperature programmed desorption and infrared spectroscopy (DRIFTS) showed that increased surface basicity caused by Li addition strains the formate intermediate to favor the dehydrogenation/decarboxylation route by strengthening -OOC bonding to the catalyst surface and weakening the C-H bond. Higher levels of Li tended to exacerbate Pt sintering (TEM), interact directly with Pt (XPS, DRIFTS of adsorbed CO), and inhibit CO<sub>2</sub> product desorption due to excessive basicity. The optimum formulation was found to be 0.54 wt% Li.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120532"},"PeriodicalIF":4.8,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144932992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Design of Experiments: A valuable tool for fine-tuning catalytic performances of Ce-UiO-67 for the allylic partial oxidation of cyclohexene 实验设计：Ce-UiO-67对环己烯烯丙基部分氧化的催化性能有价值的微调工具

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-31 DOI: 10.1016/j.apcata.2025.120534

Valeria Finelli , Federico Panagini , Reza K. Abasabadi , Francesca Rosso , Barbara Centrella , Matteo Signorile , Silvia Bordiga

{"title":"Design of Experiments: A valuable tool for fine-tuning catalytic performances of Ce-UiO-67 for the allylic partial oxidation of cyclohexene","authors":"Valeria Finelli , Federico Panagini , Reza K. Abasabadi , Francesca Rosso , Barbara Centrella , Matteo Signorile , Silvia Bordiga","doi":"10.1016/j.apcata.2025.120534","DOIUrl":"10.1016/j.apcata.2025.120534","url":null,"abstract":"<div><div>Cyclohexene allylic partial oxidation is currently a relevant reaction yielding 2-cyclohexenol and 2-cyclohexenone, that are widely used intermediates in chemical industry. The reaction is presently performed in an uncatalyzed way and, due to the radical mechanism, the control on products selectivity and overall conversion is not optimal. In this contribution, we attempted to shift cyclohexene oxidation toward a heterogeneous catalytic process, by investigating the potential of Ce-based metal-organic frameworks as catalysts. This class of materials demonstrated promising performances in oxidation catalysis, and we focus herein on the prototypical UiO-67 framework. As an initial screening, we investigated the effect of reaction compositional variables (namely initiator and substrate amount) and oxygen partial pressure in the gas-phase on the performances under very mild conditions (room temperature and pressure). To consistently perform the assessment over this variables space, we took advantage of a Design of Experiments chemometric approach. This allowed us to significantly improve the reaction performances (<em>ca.</em> 50 % increase in overall productivity with respect to not optimized conditions from literature) by performing only a subset of all possible combinations in the variables space. This contribution represents a first step toward a rational development of a catalytic process for cyclohexene allylic oxidation, based on a robust statistical approach that will be extended in the future to the investigation of other reaction parameters.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120534"},"PeriodicalIF":4.8,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145027131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Surface modification of nanocatalysts via ion beam techniques for enhanced activity 利用离子束技术对纳米催化剂进行表面改性以提高活性

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-31 DOI: 10.1016/j.apcata.2025.120536

Hanna Solt , Marina Maddaloni , Philippe Bazin , Damien Aureau , Arnaud Etcheberry , Denis Busardo , Séverine Rousseau , Gilbert Blanchard , Najat Moral , Alina Bruma , Sylvie Malo , Marco Daturi , Nancy Artioli

{"title":"Surface modification of nanocatalysts via ion beam techniques for enhanced activity","authors":"Hanna Solt , Marina Maddaloni , Philippe Bazin , Damien Aureau , Arnaud Etcheberry , Denis Busardo , Séverine Rousseau , Gilbert Blanchard , Najat Moral , Alina Bruma , Sylvie Malo , Marco Daturi , Nancy Artioli","doi":"10.1016/j.apcata.2025.120536","DOIUrl":"10.1016/j.apcata.2025.120536","url":null,"abstract":"<div><div>Interface science is at the forefront of advanced materials design, particularly in catalysis, where surface properties critically determine performance. Among emerging techniques, ion beam irradiation has shown strong potential for modifying the catalytic behavior of solid materials by introducing surface and sub-surface defects. In this study, the effect of nitrogen ion irradiation on the catalytic and redox properties of a ceria–zirconia-based oxidation catalyst (Ce₀.₆₈Zr₀.₃₂O₂), both in its unmodified form and when combined with supported Pt nanoparticles, was systematically investigated through a series of catalytic tests (TPO/TPR), operando FTIR, HRTEM, and XPS analyses. Ion bombardment was found to induce significant modifications to nanoparticle distribution, surface morphology, and defect structure—most notably the formation of oxygen vacancies and enhanced oxygen mobility. These changes resulted in improved catalytic performance for the oxidation of light alkanes and CO, with consistent reductions in T₅₀ values and a notable increase in aging resistance. The enhanced reducibility observed, particularly in Pt-containing systems, suggests a strong impact at the metal/support interface. Overall, this work highlights post-synthesis ion irradiation as an effective tool for activating and stabilizing redox catalysts, providing new opportunities for designing durable materials for environmental and energy applications.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120536"},"PeriodicalIF":4.8,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144926186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Synergistic catalysis of PtRu oxide cluster for arene C–H bond activation PtRu氧化物簇对芳烃碳氢键活化的协同催化作用

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-29 DOI: 10.1016/j.apcata.2025.120531

Shingo Hasegawa , Shion Nakamura , Koji Harano , Ken Motokura

{"title":"Synergistic catalysis of PtRu oxide cluster for arene C–H bond activation","authors":"Shingo Hasegawa , Shion Nakamura , Koji Harano , Ken Motokura","doi":"10.1016/j.apcata.2025.120531","DOIUrl":"10.1016/j.apcata.2025.120531","url":null,"abstract":"<div><div>Oxidative coupling reactions of arenes and carboxylic acids are highly efficient molecular transformation affording aryl esters from nonactivated substrates. The conventional catalytic reactions were usually carried out with oxidants such as hypervalent iodine reagents, silver salts, organic peroxides, and persulfates. From the viewpoints of atom economy, availability, and nontoxicity, molecular oxygen (O<sub>2</sub>) is a more favorable oxidant. Catalysts for the oxidative coupling using O<sub>2</sub> as an oxidant were also reported but much less studied. In this study, we developed the PtRu oxide clusters supported on activated carbon (PtRuO<sub><em>x</em></sub>/C) by simple preparation method. The formation of PtRuO<sub><em>x</em></sub> with mean diameter of 1.1 nm was clarified by using AC-HAADF-STEM, EDS, XAS, and XPS. It was found that the catalytic activity of PtRuO<sub><em>x</em></sub>/C for the acetoxylation of benzene using O<sub>2</sub> oxidant was enhanced by the synergistic effect between Pt and Ru. Kinetic measurements and DFT calculations indicated that the arene C–H bond activation proceeded by electrophilic concerted metalation deprotonation mechanism and that the surface Pt atom of PtRuO<sub><em>x</em></sub> mainly acted as the active site for the C–H bond activation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120531"},"PeriodicalIF":4.8,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Activating Fe3 single clusters for efficient electrocatalytic nitrate reduction reaction by tuning metal-support effect: A DFT study 通过调节金属支撑效应激活Fe3单团簇进行高效电催化硝酸还原反应：DFT研究

IF 4.8 2区化学

Applied Catalysis A: General Pub Date : 2025-08-28 DOI: 10.1016/j.apcata.2025.120530

Haoyu Wang , Xinyuan Yang , Shudi Ying , Riming Hu , Ruochen Zhu , Liang Xue , Xiuxian Zhao , Jiayuan Yu , Panpan Zhao , Jiachen Ma , Xuchuan Jiang

{"title":"Activating Fe3 single clusters for efficient electrocatalytic nitrate reduction reaction by tuning metal-support effect: A DFT study","authors":"Haoyu Wang , Xinyuan Yang , Shudi Ying , Riming Hu , Ruochen Zhu , Liang Xue , Xiuxian Zhao , Jiayuan Yu , Panpan Zhao , Jiachen Ma , Xuchuan Jiang","doi":"10.1016/j.apcata.2025.120530","DOIUrl":"10.1016/j.apcata.2025.120530","url":null,"abstract":"<div><div>Electrocatalytic nitrate reduction reaction (NO<sub>3</sub>RR) represents a promising green and efficient pathway for ammonia synthesis, owing to its mild reaction conditions. However, significant technological challenges persist in developing electrocatalysts capable of achieving high-selectivity ammonia synthesis. In this study, density functional theory computations are employed to investigate the performance of Fe<sub>3</sub> clusters supported on ten carbon-based substrates (Fe<sub>3</sub>/g-X, <em>X</em> = graphene (gra), GDY, N, CN, C<sub>2</sub>N, C<sub>3</sub>N, C<sub>7</sub>N<sub>3</sub>, C<sub>9</sub>N<sub>4</sub>, C<sub>10</sub>N<sub>3</sub>, and C<sub>13</sub>N<sub>3</sub>) in NO<sub>3</sub>RR. By evaluating key indicators such as structural stability, adsorption configuration, reaction mechanisms, catalytic activity, and product selectivity, it was found that Fe<sub>3</sub>/g-gra demonstrates exceptional catalytic performance under ambient conditions, with a limiting potential of only −0.51 V, and the ability to stably and selectively reduce nitrate to ammonia. Electronic structure analysis elucidates the intrinsic mechanism behind the high activity of this catalyst. Further comparative studies reveal that among Fe<sub>1</sub> to Fe<sub>4</sub> cluster catalysts (Fe<sub>n</sub>/g-gra, <em>n</em> = 1–4), Fe<sub>3</sub>/g-gra consistently maintains the optimal catalytic performance. These findings not only deepen the understanding of the metal-support effect but also provide significant theoretical and technical guidance for the development of efficient ammonia synthesis electrocatalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120530"},"PeriodicalIF":4.8,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144921489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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