Journal of Catalysis最新文献

Harnessing metal-support interaction on Pt/TiO2 catalysts for oxygen vacancy engineering via H2 reduction toward low-temperature ethylene oxidation 利用Pt/TiO2催化剂上的金属-载体相互作用进行氢还原低温乙烯氧化氧空位工程

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-11 DOI: 10.1016/j.jcat.2025.116469

Xue Kang, Wujie Guo, Tie Yu, Chen Wang

{"title":"Harnessing metal-support interaction on Pt/TiO2 catalysts for oxygen vacancy engineering via H2 reduction toward low-temperature ethylene oxidation","authors":"Xue Kang, Wujie Guo, Tie Yu, Chen Wang","doi":"10.1016/j.jcat.2025.116469","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116469","url":null,"abstract":"The Mars-van Krevelen (MvK) mechanism is widely recognized for enabling ethylene oxidation over Pt-oxide catalysts, which plays a key role in fruit and vegetable preservation. However, whether interfacial engineering can effectively promote low-temperature ethylene removal remains unclear. Herein, we systematically tuned the metal-support interaction in 2 % Pt/TiO2 catalysts via hydrogen reduction at different temperatures to construct a series of catalysts with distinct structural and electronic properties. Structural characterizations including HR-TEM and CO chemisorption revealed that increased reduction temperature led to progressive TiO2 encapsulation of Pt nanoparticles, decreasing Pt dispersion and altering the surface geometry. Meanwhile, XPS and H2-TPR analyses confirmed the generation of Ti3+ species and surface oxygen vacancies, both of which increased with reduction temperature. Kinetic studies revealed a bifunctional mechanism in which metallic Pt served as the primary site for ethylene activation, while oxygen vacancies facilitated O2 dissociation and functioned as the rate-determining step. Catalytic evaluation demonstrated that an optimal balance between Pt dispersion and oxygen vacancy concentration enabled stable and efficient ethylene conversion under ambient conditions. This study provides a mechanistic basis to manipulate metal-support interactions and engineer bifunctional active sites, offering valuable guidance for the rational design of low-temperature oxidation catalysts in practical ethylene removal applications.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"72 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145261482","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

Lewis acid sites modulate local pH of Cu for efficient electrocatalytic CO2 reduction to C2+ products 路易斯酸位点调节Cu的局部pH值，以有效地电催化CO2还原为C2+产物

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-10 DOI: 10.1016/j.jcat.2025.116475

Guoqing Song, Xin Chen, Jinhua Ye, Lequan Liu

{"title":"Lewis acid sites modulate local pH of Cu for efficient electrocatalytic CO2 reduction to C2+ products","authors":"Guoqing Song, Xin Chen, Jinhua Ye, Lequan Liu","doi":"10.1016/j.jcat.2025.116475","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116475","url":null,"abstract":"Electrocatalytic carbon dioxide reduction reaction (CO2RR) offers a promising pathway to achieve carbon neutrality. For CO2RR, alkaline electrolytes not only suppress the hydrogen evolution reaction (HER) but also facilitate the formation of multi-carbon (C2+) products. However, alkaline electrolytes react with CO2 and continuously generate carbonates, which leads to poor carbon conversion and stability. Herein, CeO2 enriched with Lewis acid sites was incorporated into Cu catalyst to modulate local pH near Cu and promote C2+ formation in neutral electrolyte. In situ pH detection measurements including Raman spectroscopy and rotating ring-disk electrode demonstrate the elevated local pH at the vicinity of Cu induced by the addition of Lewis acid sites during CO2RR, while in situ spectroscopy combined with experiments design reveal the role of high local pH in promoting C2+ selectivity. Through this design for modulating local pH, CO2 is converted into C2+ products with high Faradaic efficiency (FEC2+) of 80.5 % at 750 mA cm−2, outperforming most reported Cu-based electrocatalysts in neutral electrolyte flow cells. This work provides a feasible approach to regulate the local microenvironment at the catalyst-electrolyte interface and stabilize key intermediates to enhance the generation of C2+ products.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"39 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255485","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

Oxygen vacancies modulate reactive oxygen species for high-efficiency photocatalytic synthesis of 2,5-furandicarboxylic acid 氧空位调节活性氧在高效光催化合成2,5-呋喃二羧酸中的作用

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-10 DOI: 10.1016/j.jcat.2025.116472

Runqing Xiao, Weichen Zhao, Qingmao Yang, Anyan He, Xiaojin Tang, Chun Shen

{"title":"Oxygen vacancies modulate reactive oxygen species for high-efficiency photocatalytic synthesis of 2,5-furandicarboxylic acid","authors":"Runqing Xiao, Weichen Zhao, Qingmao Yang, Anyan He, Xiaojin Tang, Chun Shen","doi":"10.1016/j.jcat.2025.116472","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116472","url":null,"abstract":"The selective photocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) represents a promising approach to tackle increasing carbon management and climate challenges, but an insurmountable challenge lies in achieving efficient conversion at high substrate concentrations. Herein, Au/TiO2 catalysts with tunable oxygen vacancy (Ov) concentrations have been successfully prepared through adjusting the calcination atmospheres (air or H2), and serve as a platform to elucidate the critical role of Ov in selective HMF photo-oxidation. Specifically, thermal treatment under H2 atmosphere induces the escape of oxygen atoms from the TiO2 crystal structure, generating beneficial Ov defects that substantially enhance photocatalytic performance. Notably, the Ov-rich Au/TiO2-H2 catalyst demonstrates remarkably enhanced photocatalytic performance under challenging 500 mM HMF substrate concentration — achieving an exceptional FDCA yield of 97.0 % after 20 h of visible-light irradiation. Combined characterizations and experiments demonstrate the paramount role of 1O2 in hydroxyl group oxidation (rate-limiting phase). Besides, it has been conclusively demonstrated that Ov sites fulfill a dual-purpose catalytic function in 1O2 generation: facilitating the separation and migration of photo-induced charge carriers by functioning as electron trapping centers, while simultaneously facilitating the conversion of O2 molecules to generate reactive oxidative intermediates. The significance of this investigation extends beyond merely advancing our mechanistic comprehension of defect-mediated photocatalysis—it presents a viable methodology for the rational construction of high-performance catalytic materials tailored for photochemical selective oxidation transformations.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"109 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255490","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

DB-FTIR spectroscopy unravels confinement-driven modulation of Cu species in zeolite catalysts for low-temperature NH3-SCR of NOx DB-FTIR光谱揭示了低温NH3-SCR催化NOx的沸石催化剂中Cu物种的禁闭驱动调制

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-10 DOI: 10.1016/j.jcat.2025.116473

Jiachen Wang, Jiawei Cheng, Siyang Yan, Limin Ren, Yu Xu, Chunyan Liu, Zhaomin Gao, Ronghe Lin, Jiaxu Liu

{"title":"DB-FTIR spectroscopy unravels confinement-driven modulation of Cu species in zeolite catalysts for low-temperature NH3-SCR of NOx","authors":"Jiachen Wang, Jiawei Cheng, Siyang Yan, Limin Ren, Yu Xu, Chunyan Liu, Zhaomin Gao, Ronghe Lin, Jiaxu Liu","doi":"10.1016/j.jcat.2025.116473","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116473","url":null,"abstract":"The confinement of active sites within zeolite frameworks critically governs the performance of Cu-based catalysts for low-temperature ammonia selective catalytic reduction (NH3-SCR) of NOx, but the mechanistic insights regarding the nature of active Cu species remain elusive. Here, we systematically elucidate the topology-driven modulation of Cu species by integrating advanced characterizations, including X-ray absorption spectroscopy, in situ dual-beam Fourier transform infrared spectroscopy, low-temperature CO/NO adsorption, and catalytic evaluations across Cu-SSZ-13, Cu-ZSM-5, Cu-Beta, and oxide-supported analogues. We demonstrate that, i) in comparison to MFI and BEA topologies, the strong spatial confinement within the CHA framework preferentially forms most abundant Cu+ sites with low-coordination numbers to carbonyl species, and stabilizes Z2Cu2+ species in six-membered rings, enhancing Cu+/Cu2+ redox cycle and thus NO adsorption and nitrate turnover efficiency. ii) The ion-exchange and one-pot synthesis methods strongly influence the distribution and location Cu2+ species in Cu-SSZ-13 that further influence the activity. Mechanistic insights from in situ spectroscopy reveal that topology-governed Cu speciation dictates the formation and consumption of critical nitrate intermediates, enabling efficient low-temperature SCR cycles. These findings not only establish a clear topology-activity relationship for Cu-containing zeolite catalysts but also offer a mechanistic blueprint for the rational design of catalysts, advancing NOx abatement technologies to meet increasingly stringent emission regulations.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"122 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255492","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

Microkinetic modelling of post-plasma catalysis to improve the conversion of dry reforming of methane in a gliding arc plasmatron 等离子体后催化提高甲烷在滑行弧等离子体中干重整转化的微动力学模型

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-10 DOI: 10.1016/j.jcat.2025.116474

Sara Ceulemans, Eduardo Morais, Björn Loenders, Annemie Bogaerts

{"title":"Microkinetic modelling of post-plasma catalysis to improve the conversion of dry reforming of methane in a gliding arc plasmatron","authors":"Sara Ceulemans, Eduardo Morais, Björn Loenders, Annemie Bogaerts","doi":"10.1016/j.jcat.2025.116474","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116474","url":null,"abstract":"Plasma conversion of the greenhouse gases CO2 and CH4 into useful products via dry reforming of methane (DRM) has shown promising results in gliding arc and other warm plasmas, but the conversions and product distribution can be further improved. In this work, we investigate the effects of adding a post-plasma Ni catalyst, to achieve extra CO2 and CH4 conversion via the catalytic DRM reaction. We developed a 0D microkinetic model to calculate gas-phase and surface reactions in the plasma, afterglow, and catalyst surface, which can be used to study both conversion trends, as well as the underlying reaction mechanisms. We examined a range of relevant parameters, and the results show an improvement in conversion, especially at high catalyst site density, catalyst bed gas temperature and fraction of gas converted by the plasma. At the optimal 30/70 CO2/CH4 input gas mixture, our model predicts an increase in conversion from 25 %, to 68 % and 43 % for CO2 and CH4, respectively, upon Ni catalyst addition. The pathway analysis reveals that adsorbed C atoms (C*) play a critical role, and upon recombination with O* into CO*, they link the CO2 and CH4 conversion mechanisms, albeit a balance must be maintained to avoid C*-poisoning. In addition, the pathway depends on the Ni facet, with most conversion taking place on Ni(1 1 0). Overall, our model demonstrates the positive effects of integrating post-plasma catalysis to a warm plasma, guiding experimental work to obtain the highest possible conversions, by tuning the input conditions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"69 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255487","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

Theoretical study on Rh metal catalyst in NO–CO reaction: Significant surface dependences of activity and selectivity Rh金属催化剂在NO-CO反应中的理论研究：活性和选择性的显著表面依赖性

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-08 DOI: 10.1016/j.jcat.2025.116471

Jun-Qing Yin, Yan-Ping Zhang, Takahito Nakajima, Shigeyoshi Sakaki

{"title":"Theoretical study on Rh metal catalyst in NO–CO reaction: Significant surface dependences of activity and selectivity","authors":"Jun-Qing Yin, Yan-Ping Zhang, Takahito Nakajima, Shigeyoshi Sakaki","doi":"10.1016/j.jcat.2025.116471","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116471","url":null,"abstract":"Surface-dependences of catalytic activity and selectivity of metal-particle are crucial for understanding catalysis and designing new catalysts. However, correct knowledge is limited. Herein, Rh metal catalyst for NO–CO reaction is investigated using DFT calculations with microkinetic simulation to elucidate surface-dependences of activity and selectivity. Reactivity for N‒O bond cleavage decreases in the order Rh(100) > Rh(110) ∼ Rh(211) ∼ Rh(311) > Rh(210) > Rh(331) ∼ Rh(111). Reactivity for CO2 formation decreases in the order Rh(100) > Rh(331) > Rh(110) ∼ Rh(111) > Rh(311) ∼ Rh(211) ∼ Rh(210). Reactivity for N2O formation decreases in the order Rh(100) ∼ Rh(210) ∼ Rh(331) > Rh(110) > Rh(111) > Rh (211) > Rh(311). N2 formation from N2O via N2‒O bond cleavage is not easy to occur in almost all surfaces due to small N2O desorption energy except Rh(210). Reactivity for N2 formation via recombination of two adsorbed N atoms (named 2 N recombination) decreases in the order Rh(110) > Rh(211) > Rh(100) > Rh(331) > Rh(311) > Rh(210) > Rh(111). Microkinetic simulation using these computational results indicates that Rh(100), Rh(110), Rh(211), and Rh(311) surfaces are active for NO–CO reaction at both low and high temperatures but the thermodynamically most stable Rh(111) surface is active only at high temperature. Rh metal particle with Rh(100), Rh(110), Rh(211), and/or Rh(311) facets is proposed as excellent catalyst, whereas Rh metal particle with Rh(111), Rh(210), and/or Rh(331) facets is not. Considering exposure ratios of facets, Rh metal particle with Rh(100) and/or Rh(311) is recommended as a promising catalyst.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"86 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247202","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

Strong metal support interaction driven synthesis of ultrasmall high entropy alloy nanoparticles for selective hydrogenation 强金属载体相互作用驱动的超小高熵合金纳米颗粒选择性加氢合成

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-08 DOI: 10.1016/j.jcat.2025.116468

Ren Tu, Hui Yang, Yan Sun, Kaili Liang, Bingsen Zhang, Charles Q. Jia, Shixian Wang, Yujian Wu, Xudong Fan, Enchen Jiang, Xiwei Xu

{"title":"Strong metal support interaction driven synthesis of ultrasmall high entropy alloy nanoparticles for selective hydrogenation","authors":"Ren Tu, Hui Yang, Yan Sun, Kaili Liang, Bingsen Zhang, Charles Q. Jia, Shixian Wang, Yujian Wu, Xudong Fan, Enchen Jiang, Xiwei Xu","doi":"10.1016/j.jcat.2025.116468","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116468","url":null,"abstract":"High-entropy alloys (HEAs) have garnered significant attention due to their nearly infinite number of unprecedented active sites. However, the synthesis of ultrasmall HEA nanoparticles remains challenging due to their inherent thermodynamic instability. In this study, we demonstrate that a strong metal-support interaction (SMSI) can effectively suppress agglomeration through interfacial stabilization. By leveraging a quenching-based approach, we successfully synthesized HEA catalysts with ultralow loading (<0.17 wt%), ultrasmall particle sizes (<3.7 nm), and an SMSI-induced encapsulation layer. The formation of this protective layer enables precise control over the structural and electronic properties of catalyst. To probe the catalytic performance, cinnamaldehyde was employed as a model α,β-unsaturated aldehyde in selective hydrogenation reactions. The results reveal that a lower Pt ratio in HEA-Cu8Pt2 enhances HCAL selectivity, reaching 93.6 %, which is attributed to the modified interfacial electronic environment between TiO2 and HEA, promoting Pt2+ species formation and strong hydrogen spillover. This work provides new insights into the design and regulation of ultrasmall HEA catalysts through SMSI effects.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247200","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

Pentaerythritol structure-directing agents bias aluminum siting in MFI zeolites to increase para-xylene selectivity during toluene methylation 季戊四醇结构导向剂在MFI沸石中偏置铝以增加甲苯甲基化过程中对二甲苯的选择性

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2025-10-07 DOI: 10.1016/j.jcat.2025.116470

Andrew T. Norfleet, Sopuruchukwu Ezenwa, David Hibbitts, Rajamani Gounder

引用次数: 0

CeO2/H-SSZ-13 composite NH3-SCR catalysts achieve unprecedented high-temperature N2 selectivity CeO2/H-SSZ-13复合NH3-SCR催化剂实现了前所未有的高温N2选择性

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-07 DOI: 10.1016/j.jcat.2025.116459

Zhiying Liu , Meiqing Shen , Shuhuan Wang , Chunjuan Zhang , Gurong Shen , Xinhua Li , Wei Li , Feng Gao

{"title":"CeO2/H-SSZ-13 composite NH3-SCR catalysts achieve unprecedented high-temperature N2 selectivity","authors":"Zhiying Liu , Meiqing Shen , Shuhuan Wang , Chunjuan Zhang , Gurong Shen , Xinhua Li , Wei Li , Feng Gao","doi":"10.1016/j.jcat.2025.116459","DOIUrl":"10.1016/j.jcat.2025.116459","url":null,"abstract":"<div><div>A series of CeO2/H-SSZ-13 composite catalysts with CeO2 contents ranging from 5 to 50 wt% are investigated. The catalysts are characterized using various techniques, including XRD, SEM, TEM, XPS, H2-TPR, Raman spectroscopy and chemical titrations coupled with TPD and DRIFTS. Their catalytic performance is evaluated through steady-state NH3-SCR. DFT calculations are also applied to supplement experimental data. The results demonstrate that the synergistic interactions between the redox domain (CeO2) and the acid domain (H-SSZ-13) render the composite catalysts with excellent medium-to-high-temperature deNOx efficiency. Notably, the formation of the unwanted N2O side product is completely eliminated over these composite catalysts. By systematically regulating redox and acid functions, it is revealed that CeO2 serves as the key active component for the rate-determining NO activation step, while H-SSZ-13 facilitates NH3 adsorption and the decomposition of reactive intermediates. Based on detailed studies of SCR kinetics, N2O formation, chemical trapping, as well as DFT calculations, it is proposed that the gaseous nitrite precursor HONO acts as the key reaction intermediate.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116459"},"PeriodicalIF":6.5,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235256","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

Regulation of remote sites to enhance Pt activity in the hydrogenation of sulfur-containing nitroarenes 调控远程位点以增强含硫硝基芳烃加氢过程中的铂活性

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-10-07 DOI: 10.1016/j.jcat.2025.116461

Haitao Chen , Zongpeng Ling , Jie Yu , Tao Cheng , Xuefang Zhao , Yunuo Chen , Xin Liu , Zhenchao Zhao , Qihua Yang

{"title":"Regulation of remote sites to enhance Pt activity in the hydrogenation of sulfur-containing nitroarenes","authors":"Haitao Chen , Zongpeng Ling , Jie Yu , Tao Cheng , Xuefang Zhao , Yunuo Chen , Xin Liu , Zhenchao Zhao , Qihua Yang","doi":"10.1016/j.jcat.2025.116461","DOIUrl":"10.1016/j.jcat.2025.116461","url":null,"abstract":"<div><div>Outer-sphere catalysis, commonly associated with enzyme and homogeneous catalysis, utilizes remote sites to drive reactions and is particularly effective for reactants that are toxic to the catalyst. However, this approach has been rarely explored in heterogeneous catalysis. In this study, we demonstrate the use of remote sites to enhance the activity of Pt nanoparticles (NPs) in the hydrogenation of sulfur-containing nitroarenes. Catalysts with Pt and MoO3 co-deposited on TiO2 efficiently catalyze the hydrogenation of 5-nitrobenzothiazole (NBZ) under mild conditions, achieving a conversion rate of 5448 molNBZ · molPt−1 · h−1, the highest reported to date, even with ppm levels of Pt. The optimized Pt density (∼3 NPs per 1 × 104 nm2) on the catalyst was found to favor HxMoO3 mediated sequential H transfer from Pt to Mo and subsequently to the substrate. While higher Pt density may enhance H transfer to Mo, the hydrogenation process becomes limited by the availability of HxMoO3 for further H transfer to the substrate, revealing the intrinsic reason for the high activity of catalysts with ppm Pt. A direct transfer of intercalated H in HxMoO3 to the substrate, rather than solvent-mediated proton-coupled electron transfer (PCET) dominating the hydrogenation, was observed and confirmed through solvent isotope kinetic effects and solvent studies. Tuning remote sites on solid catalysts offers a promising strategy for developing catalysts with the minimize the use of precious metals in the hydrogenation of strongly coordinating reactants.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"453 ","pages":"Article 116461"},"PeriodicalIF":6.5,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235309","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