Henry Martínez , Álvaro A. Amaya , Fernando Martínez O. , Cecilia C. Torres , Cristian H. Campos
{"title":"Selective photo-oxidation of lignin-based alcohols to aldehydes catalyzed by gold nanoparticles supported on titanate nanotubes and nanowires","authors":"Henry Martínez , Álvaro A. Amaya , Fernando Martínez O. , Cecilia C. Torres , Cristian H. Campos","doi":"10.1016/j.apcata.2025.120410","DOIUrl":"10.1016/j.apcata.2025.120410","url":null,"abstract":"<div><div>Photocatalytic conversion of biomass and its derivatives is a promising strategy for producing energy and products of industrial interest. In this study, the selective photooxidation of lignin-derived alcohols (vanillyl and veratryl) to their respective aldehydes was investigated using gold nanoparticles (AuNPs) supported on hydrogen titanate nanotubes (HTNTs) and nanowires (HTNWs) under visible light and O<sub>2</sub> at room temperature and pressure. The results show that the AuNPs/HTNTs and AuNPs/HTNWs systems are highly active and selective in the photooxidation of vanillyl and veratryl alcohol, with conversions above 90 % and selectivity above 95 % toward the formation of vanillin and veratraldehyde, respectively. The preparation of the photocatalytic systems by functionalization with (3-aminopropyl)trimethoxysilane and subsequent deposition–reduction with NaBH<sub>4</sub> of Au in successive cycles allowed us to obtain metal loadings of 1, 3 %, and 5 % by mass, controlling the size, dispersion, and stability of the nanoparticles AuNPs. Physicochemical characterization of the solids showed that the incorporation of AuNPs into HTNT and HTNW supports led to an increase in oxygen vacancies, a decrease in the charge transfer resistance of the material, and thus a lower recombination rate of electron–hole pairs. Further studies in the presence of scavenger molecules and electron paramagnetic spectroscopy allowed us to conclude that under visible light, the AuNPs generate photoelectrons that move toward the conduction band of the support, where the reduction of O<sub>2</sub> occurs to form the superoxide radical anion, the main reactive oxygen species causing the oxidation of alcohols.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120410"},"PeriodicalIF":4.7,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144491187","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}
Astrid Kjær Steffensen, Wenting Fang , Leonhard Schill, Sebastian Meier, Anders Riisager
{"title":"Furfural oxidation by hierarchical titanium silicate catalyst with NiO nanoparticles: Improved diacid yield and elucidation of reaction pathway","authors":"Astrid Kjær Steffensen, Wenting Fang , Leonhard Schill, Sebastian Meier, Anders Riisager","doi":"10.1016/j.apcata.2025.120409","DOIUrl":"10.1016/j.apcata.2025.120409","url":null,"abstract":"<div><div>Oxidation of biomass-derived furfural with hydrogen peroxide provides a sustainable path to 1,4-diacids for polymer production. The state-of-the-art catalyst, titanium silicate (TS-1), suffers from drawbacks including deactivation and diffusion limitations, but its catalytic activity can be improved by introducing mesoporosity and metal species. Herein, hierarchical TS-1 (HTS-1) catalysts loaded with different metal oxides were prepared and examined for furfural oxidation with aqueous hydrogen peroxide. HTS-1 loaded with Ni (Ni/HTS-1) yielded 32 % maleic acid from furfural under screening conditions, which was 28 % higher relative yield than unloaded HTS-1 under the same conditions. Catalyst characterization and an <em>in situ</em> <sup>13</sup>C NMR study elucidated the promotional role of Ni and the pathway, by which the reaction proceeds. Surprisingly, the NMR study indicated that the reactions using both Ni/HTS-1 and unloaded HTS-1 proceed <em>via</em> formation of furfural peroxide followed by Baeyer-Villiger oxidation, and not <em>via</em> epoxidation as many other TS-1 catalyzed oxidations.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120409"},"PeriodicalIF":4.7,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144321497","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}
Xiyan Yue , Hongyun Liang , Yinsong Zhang , Yaoqi Zhou , Jiajia Wang , Zhengkun Xie , Peng Yang , Yufei Ma , Xiumin Li
{"title":"Fabrication of FeCoNi LDH medium entropy hydroxide nanosheet for catalyzing oxygen evolution reaction","authors":"Xiyan Yue , Hongyun Liang , Yinsong Zhang , Yaoqi Zhou , Jiajia Wang , Zhengkun Xie , Peng Yang , Yufei Ma , Xiumin Li","doi":"10.1016/j.apcata.2025.120408","DOIUrl":"10.1016/j.apcata.2025.120408","url":null,"abstract":"<div><div>Medium entropy material-based catalysts have garnered increasing attention in water electrolysis due to their high electrocatalytic activity and excellent stability, which are attributed to lattice distortion and hysteretic diffusion effects. In this study, we successfully fabricated 3D nanoflower-like array of FeCoNi layered double medium entropy hydroxide (ME-LDH) nanosheets for the oxygen evolution reaction (OER) through a one-step hydrothermal synthesis method. Subsequently, the FeCoNi LDH was activated via NaClO oxidation treatment, thereby modulating the valence states of the metallic elements. The performance of the activated FeCoNi LDH (A-FeCoNi LDH) was further optimized by precisely adjusting the hydrothermal temperature and metal ion concentration. Benefiting from its unique nanostructure, lattice distortion, and multiple active sites, the A-FeCoNi LDH coated electrode demonstrates superior OER electrocatalytic performance, achieving a low overpotential of 228 mV and a low Tafel slope of 58.37 mV dec<sup>−1</sup> to deliver a current density of 10 mA cm<sup>−2</sup>, along with remarkable long-term stability exceeding 80 h. This work provides an innovative strategy for developing efficient medium entropy electrocatalysts, showcasing significant potential for practical industrial applications.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120408"},"PeriodicalIF":4.7,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144298730","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}
Arvind Kumar , Wilson Sue Chee Ming , Padminee Ramsaroop , Shobha Abigail Dhanpat , Michael Forde , Dinesh Pathak , Vinod Kumar
{"title":"Leveraging vanadium and H2O2 as green oxidant in functionalisation of organic molecules","authors":"Arvind Kumar , Wilson Sue Chee Ming , Padminee Ramsaroop , Shobha Abigail Dhanpat , Michael Forde , Dinesh Pathak , Vinod Kumar","doi":"10.1016/j.apcata.2025.120406","DOIUrl":"10.1016/j.apcata.2025.120406","url":null,"abstract":"<div><div>Vanadium catalysts paired with hydrogen peroxide (H₂O₂) as a green oxidant offer a versatile and sustainable platform for the selective oxidative functionalization of organic molecules. This review provides a comprehensive survey of recent advances in vanadium–H₂O₂ catalysis across essential transformations, namely epoxidation, oxidative cleavage of C<img>C bonds, oxidation of alcohol, C–H bond activation, sulfide oxidation, halogenation, and tandem oxidative processes. Emphasis is placed on how ligand design particularly Schiff base ligands and polyoxometalates tunes catalytic activity, selectivity, and stability. The role of reactive vanadium species, such as mono- and peroxovanadates along with mechanistic insights, structure–activity relationships, and the influence of solvent and oxidant control are discussed. Sustainability is evaluated using green chemistry metrics including atom economy, E-factor, process mass intensity (PMI), turnover number (TON), and turnover frequency (TOF). Despite notable progress, challenges such as catalyst deactivation, limited efficacy in unactivated C–H oxidations, and insufficient mechanistic resolution persist. This review concludes by highlighting emerging strategies in ligand design and reactor engineering, positioning vanadium–H₂O₂ systems as promising platforms for scalable, efficient, and sustainable oxidation chemistry.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120406"},"PeriodicalIF":4.7,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338722","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}
Yunfei Zhang , Jun Liu , Xiaodi Zhang , Ying Wang , Yuqiong Zhao , Dong Shen , Guoqiang Li , Guojie Zhang
{"title":"Pore structure and oxygen vacancies synergy: Advancements in Ni/MSS@CeO2 catalysts for efficient DRM","authors":"Yunfei Zhang , Jun Liu , Xiaodi Zhang , Ying Wang , Yuqiong Zhao , Dong Shen , Guoqiang Li , Guojie Zhang","doi":"10.1016/j.apcata.2025.120407","DOIUrl":"10.1016/j.apcata.2025.120407","url":null,"abstract":"<div><div>The low-temperature carbon deposition resistance of Ni-based DRM catalysts supported on inert SiO<sub>2</sub> can be improved by constructing oxygen vacancies. This work deeply explored the role of monodispersed mesoporous silica spheres (MSS) and non-porous SiO<sub>2</sub> support layer structure on the structure and oxygen vacancies of sandwich Ni/MSS@CeO<sub>2</sub> and Ni/SiO<sub>2</sub>@CeO<sub>2</sub> catalysts and their catalytic performance. The results show that Ce<sub>9.33</sub>(SiO<sub>4</sub>)<sub>6</sub>O<sub>2</sub> generated by high-temperature H<sub>2</sub> reduction greatly increases the number of oxygen vacancies. In comparison to non-porous SiO<sub>2</sub>, the dual confinement effect of MSS's pore and CeO<sub>2</sub> shell layer prevented Ni particles from sintering. The unique pore of MSS promotes the dispersion of Ni and CeO<sub>2</sub>, constructing more Ni-O-Ce active sites and enhancing the Ni-CeO<sub>2</sub> interaction. It has low activation energy for decomposition of CH<sub>4</sub> and CO<sub>2</sub>. In addition, the oxygen vacancies provided by the CeO<sub>2</sub> shell notably inhibit carbon deposition and reduce the degree of graphitization. Ni/SiO<sub>2</sub>@CeO<sub>2</sub> has more oxygen vacancies, but due to the high crystallinity, weak redox ability and strong thermal stability of Ce<sub>9.33</sub>(SiO<sub>4</sub>)<sub>6</sub>O<sub>2</sub>, the oxygen vacancies it produces cannot fully activate CH<sub>4</sub> and CO<sub>2</sub>, and also cover some active sites of Ni. Ni/MSS@CeO<sub>2</sub> resulted in minimal carbon deposits during a 30 h reaction under low-temperature and high space velocity. In situ DRIFT technology confirmed that Ni/MSS@CeO<sub>2</sub> follows the HCOO* pathway. The oxygen species can react with the carbon species produced by CH<sub>4</sub> decomposition. This work offers valuable insights for the design of efficient Ni-SiO<sub>2</sub>-CeO<sub>2</sub> catalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120407"},"PeriodicalIF":4.7,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279464","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}
Jin Guo , Xueying Bai , Xianquan Li , Jifeng Pang , Lele Feng , Yujia Zhao , Yang Su , Shimin Liu , Chaoqian Liu , Mingyuan Zheng
{"title":"Stabilizing copper particles by silanol nests on modified silicalite-1 for ethanol dehydrogenation","authors":"Jin Guo , Xueying Bai , Xianquan Li , Jifeng Pang , Lele Feng , Yujia Zhao , Yang Su , Shimin Liu , Chaoqian Liu , Mingyuan Zheng","doi":"10.1016/j.apcata.2025.120405","DOIUrl":"10.1016/j.apcata.2025.120405","url":null,"abstract":"<div><div>Copper(Cu)-based catalysts are highly promising candidates for ethanol dehydrogenation owing to their exceptional activity in cleaving O-H and C-H bonds. Nevertheless, their widespread application is hindered by challenges such as rapid deactivation and complex preparation procedures. Herein, inspired by the deactivation mechanism of Cu/MFI (silicalite-1) catalysts, two strategies, i.e., using mixed solvents for impregnation and enriching silanol nests of MFI to anchor Cu particles, were used to synthesize Cu/MFI-R catalysts with high stability and activity. The mixed solvent approach reduces the surface tension of solvents, enhancing the uniform dispersion of Cu over the hydrophobic surface of MFI. Subsequently, a MFI-R support with abundant silanol nests was synthesized via optimizing hydrothermal conditions, as confirmed by reaction results and characterizations of FT-IR, UV-Vis and solid NMR. By combining these strategies, Cu/MFI-R catalysts were synthesized for ethanol dehydrogenation, achieving > 90 % ethanol conversion and 95 % acetaldehyde selectivity over the 600 h time on stream test. This work provides a very promising scalable approach for the design of stable Cu-based catalysts in hydrogen-related reactions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120405"},"PeriodicalIF":4.7,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144288854","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}
Huan Zhang , Jiahui Li , Zhe Shen , Haijie Hu , Wenbo Jin , Chengtun Qu
{"title":"Recent advances of CO2 electroreduction towards ethanol over Cu-based catalysts","authors":"Huan Zhang , Jiahui Li , Zhe Shen , Haijie Hu , Wenbo Jin , Chengtun Qu","doi":"10.1016/j.apcata.2025.120404","DOIUrl":"10.1016/j.apcata.2025.120404","url":null,"abstract":"<div><div>Electrochemical reduction of CO<sub>2</sub> (ERCO<sub>2</sub>) represents a promising strategy for atmospheric CO<sub>2</sub> mitigation by converting this greenhouse gas into value-added chemical feed stocks. Among various catalytic materials, copper-based electrocatalysts have emerged as frontier candidates due to their distinctive capability in promoting C-C coupling reactions, which selectively steer the reaction pathway toward multi-carbon products. Notably, these catalysts exhibit superior performance in producing industrially important C<sub>2</sub> compounds such as ethylene and ethanol through precise modulation of reaction intermediates, thereby demonstrating significant potential for establishing a circular carbon economy. This paper provides a review of the reaction mechanism involved in the electrocatalytic reduction of CO<sub>2</sub> to ethanol. It also discusses the research progress made in the development of Cu-based catalysts for this reaction, including Cu monomers, Cu-based bimetallic catalysts, CuO-based catalysts and non-metallic modified Cu-based catalysts. Additionally, the paper introduces various strategies that have been employed to enhance the selectivity of ethanol products, such as the confinement strategy、local environment modulation and electronic structure modulation. Finally, the paper discusses the challenges and future development directions of Cu-based catalysts in the electrocatalytic reduction of CO<sub>2</sub> to ethanol.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120404"},"PeriodicalIF":4.7,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144271606","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}
Xiaomeng Yang , Jinghao Huo , Hanjun Zhu , Xin Nie , Quan Wan , Jukun Xiong , Huixian Shi
{"title":"Carbon film-modified Bi5O7I composites for highly efficient simultaneous photocatalytic removal of bisphenol-A and Cr(VI) under visible light irradiation","authors":"Xiaomeng Yang , Jinghao Huo , Hanjun Zhu , Xin Nie , Quan Wan , Jukun Xiong , Huixian Shi","doi":"10.1016/j.apcata.2025.120403","DOIUrl":"10.1016/j.apcata.2025.120403","url":null,"abstract":"<div><div>The coexistence of heavy metals and organic pollutants in aquatic ecosystems poses significant threats to environmental and human health. To address this issue, a novel carbon film-modified Bi<sub>5</sub>O<sub>7</sub>I photocatalyst (C/Bi<sub>5</sub>O<sub>7</sub>I) was developed for the simultaneous removal of bisphenol-A (BPA) and Cr(VI) under visible light. The C/Bi<sub>5</sub>O<sub>7</sub>I composite exploited the synergistic effect between the carbon film and Bi<sub>5</sub>O<sub>7</sub>I, enhancing light absorption and facilitating efficient electron transfer, which promoted the separation of electron-hole pairs. This mechanism enabled holes to degrade BPA and electrons to reduce Cr(VI), with each process mutually accelerating the other. The composite exhibited high photocatalytic activity across a wide pH range (3.0–11.0) and was minimally inhibited by typical water matrix components. Characterization techniques and theoretical calculations were employed to elucidate the degradation pathways, confirming the stability and efficiency of C/Bi<sub>5</sub>O<sub>7</sub>I over multiple cycles. This makes C/Bi<sub>5</sub>O<sub>7</sub>I a promising material for treating wastewater contaminated with coexisting heavy metals and organic pollutants.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120403"},"PeriodicalIF":4.7,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144261779","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}
Juliana Bertoldi , Camila E. Kozonoe , Éder V. Oliveira , Morgana Rosset , Larissa Otubo , Elisabete M. Assaf , Martin Schmal
{"title":"Investigation of oxygen mobility on LaNi-Zn perovskite catalyst for carbon inhibition in dry reforming of methane","authors":"Juliana Bertoldi , Camila E. Kozonoe , Éder V. Oliveira , Morgana Rosset , Larissa Otubo , Elisabete M. Assaf , Martin Schmal","doi":"10.1016/j.apcata.2025.120400","DOIUrl":"10.1016/j.apcata.2025.120400","url":null,"abstract":"<div><div>Carbon formation is one of the major problems in methane reforming reactions, mainly in dry reforming of methane (DRM), limiting its industrial competitiveness. Thus, in this work, we investigate the oxygen mobility and carbon resistance of the LaNi-Zn perovskite in the DRM reaction. The catalysts LaNiO<sub>3</sub> (LN) and LaNi<sub>0.5</sub>Zn<sub>0.5</sub>O<sub>3-δ</sub> (LNZn) were synthesized and characterized by XRD, H<sub>2</sub>-TPR, CH<sub>4</sub>-TPSR-MS, H<sub>2</sub>-TPHR-MS, XPS, TGA, Raman, HRTEM, and <em>quasi-in-situ</em> DRIFTS-MS, aiming to understand the role of the promoter in coke suppression. The CH<sub>4</sub>-TPSR-MS, H<sub>2</sub>-TPHR-MS, and Raman analyses revealed that the Zn-substituted catalyst exhibited higher oxygen mobility compared to the LN catalyst, attributed to the oxophilicity of Zn<sup>2+</sup>, which facilitates carbon gasification. XPS and HRTEM analyses of reduced samples confirmed the presence of metallic Zn<sup>0</sup> on the surface as Ni-Zn alloying. 30 h of TOS showed higher activity for the LN catalyst than the LNZn. However, post-reaction analysis indicated that the addition of Zn increased carbon resistance by 5 times. The formation of the Ni-Zn alloying effectively prevented the removal of Ni particles from the support and their encapsulation by carbon nanotubes. <em>Quasi-in-situ</em> DRIFTS-MS has revealed that the LNZn catalyst promotes the formation of intermediate species responsible for carbon oxidation (CH<sub>x</sub>O, HCOO<sup>⁻</sup>, and HCO<sub>3</sub><sup>⁻</sup>), clearing the anti-carbon behavior of the Zn-substituted catalyst.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120400"},"PeriodicalIF":4.7,"publicationDate":"2025-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144271607","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}
{"title":"Elucidating the structure-activity relationship of Bi-doped MnO2 catalysts towards CH3OH oxidation","authors":"Suxin Yu, Haoyuan Gu, Qihang Wen, Yi-Fan Han, Minghui Zhu","doi":"10.1016/j.apcata.2025.120402","DOIUrl":"10.1016/j.apcata.2025.120402","url":null,"abstract":"<div><div>MnO<sub>2</sub>-based catalysts have been extensively utilized in the catalytic oxidation of volatile organic compounds due to their cost-effectiveness. In this study, a series of Bi-doped MnO<sub>2</sub> catalysts with various contents were systematically investigated to reveal the structure-activity relationship during the CH<sub>3</sub>OH oxidation reaction, which was achieved using a series of characterizations. Bi could enter the MnO<sub>2</sub> lattice and lead to the facile formation of oxygen vacancies, facilitating the generation of surface reactive oxygen species by O<sub>2</sub> dissociation. With the increase of Bi, the activity showed a volcanic trend, and the Mn<sub>7.5</sub>Bi<sub>1</sub>O<sub>x</sub> (T<sub>90</sub> = 160 °C) exhibited the lowest apparent activation energy and optimal performance. CH<sub>3</sub>OH oxidation mechanism (CH<sub>3</sub>OH → methoxy species → formate species → CO<sub>2</sub> and H<sub>2</sub>O) was revealed by <em>in situ</em> DRIFTS, and the last two oxidation processes were significantly sped up. Bi-doped MnO<sub>2</sub> exhibited high H<sub>2</sub>O tolerance due to hydroxyl-assisted CH<sub>3</sub>OH chemisorption via hydrogen bonding and hydroxyl-assisted C-H activation of methoxy species with surface reactive oxygen species. These findings are beneficial for the rational design of metal-doped catalysts with rich oxygen vacancy defects for catalytic oxidation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"704 ","pages":"Article 120402"},"PeriodicalIF":4.7,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144254308","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}