Journal of Catalysis最新文献

{"title":"Multi-descriptors guided constructing the microenvironment of frustrated Lewis pair bi-active sites in functionalized MOFs toward Sabatier optimal for catalytic hydrogenation","authors":"Linmeng Wang ,&nbsp;Shihao Feng ,&nbsp;Hongyi Gao ,&nbsp;Yunfeng Lu ,&nbsp;Jingjing Wang ,&nbsp;Ge Wang","doi":"10.1016/j.jcat.2025.116165","DOIUrl":"10.1016/j.jcat.2025.116165","url":null,"abstract":"<div><div>Precise design and regulation of active site accessibility and chemical properties within metal–organic frameworks (MOFs) are crucial for enhancing catalytic performance, yet pose significant challenges. This study presents a design strategy for functionalized MOF-808 catalysts featuring frustrated Lewis pair (FLP) bi-active sites for catalytic hydrogenation. More specifically, we modulated the microenvironment of Lewis acid-base sites (LA-LB) by 4 categories of monocarboxylic acid ligands (i.e., the 6-substituted BR₂ piperidine-2-carboxylic acid (FLP1-R), 1-substituted BR₂ pyrazole-2-carboxylic acid (FLP2-R), 5-substituted BR₂ pyrrolidine-2-carboxylic acid (FLP3-R) and 6-substituted BR₂ pyridine-2-carboxylic acid (FLP4-R)) exchange, in which the LA coordinated the substituent group (−R) is −H, –OH, –NH₂, –CH₃, −Br, −Cl, −F, –NO₂, −CF₃, or –CN. Utilizing density functional theory (DFT), it elucidates the electronic-level regulation mechanisms affecting catalytic performance. We establish screening principles for 40 functionalized MOFs, revealing linear relationships between the geometric and electronic structures of the active moiety (neutral FLP-R) and both adsorption energy and Gibbs free energy barriers. Multi-descriptors, the dihedral angle between LA, LB and the critical points (c₁ and c₂) of electron localization function (ELF) upon dual active sites (φ_c1-LB-LA-c2), the distance of LA and LB (D_LA&amp;LB) and local chemical potential (μ_L) of FLP-R were firstly proposed to identify candidates favoring dissociative H₂ adsorption over chemisorbed dicyclopentadiene (DCPD), thereby mitigating bi-active site due to strongly bound. Furthermore, the intrinsic descriptor <span><math><mrow><msubsup><mrow><mo>|</mo><mi>ε</mi></mrow><mrow><mi>p</mi></mrow><mi>B</mi></msubsup><mrow><mo>|</mo><mo>+</mo><mo>|</mo></mrow><msubsup><mi>ε</mi><mrow><mi>p</mi></mrow><mi>N</mi></msubsup><mrow><mo>|</mo></mrow></mrow></math></span> derived by the p band center of B atom (LA) and N atom (LB) yield an inverted volcano-shaped curve, with FLP3-CH₃, FLP4-F, FLP4-CH₃, and FLP4-OH functionalized MOF-808 positioned at the optimal point, balancing H₂ dissociation and the hydrogenation of 8,9-dihydrodicyclopentadiene (8,9-DHDCPD). Our work bridges the inherent characteristics of catalysts and their catalytic activities through the development of multi-descriptors, paving the way for high-performance MOF design.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116165"},"PeriodicalIF":6.5,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultra-broad molecular weight distribution polyethylene produced by bis(imino)pyridyl cobalt catalysts","authors":"Heng Gao,&nbsp;Zonglin Qiu,&nbsp;Handou Zheng,&nbsp;Xieyi Xiao,&nbsp;Haotian Zhou,&nbsp;Chunyu Feng,&nbsp;Haiyang Gao","doi":"10.1016/j.jcat.2025.116166","DOIUrl":"10.1016/j.jcat.2025.116166","url":null,"abstract":"<div><div>As the largest amount of worldwide produced polymeric materials, the broad applicability requires polyethylene (PE) to possess good processability and mechanical properties through tailored molecular weight (MW) and molecular weight distribution (MWD). Direct synthesis of broad MWD PE with ultra-high molecular weight component is highly desirable and challenging. In this paper, a series of bis(imino)pyridyl cobalt complexes with substituted 8-(<em>p</em>-R-phenyl)naphthylamine (R = OMe, Me, H, CF₃) were designed and synthesized for ethylene polymerization. The intramolecular <em>π-π</em> interactions between the capping aryl groups and the pyridyl ring are clearly observed in bis(imino)pyridyl cobalt complexes, which are a crucial driving force for highly active ethylene polymerization. The existence of s<em>yn</em> and <em>anti</em> diastereomers of bis(imino)pyridyl cobalt complexes is also proved by single crystal X-ray diffraction analysis. The ultra-broad MWD PE (MWD &gt;100) with <em>M</em>_w from hundreds to ten million is produced, which is a cooperative result of <em>syn</em> and <em>anti</em> diastereomers of cobalt catalysts and two chain transfer pathways involving <em>β</em>-H transfer to the monomer and chain transfer to aluminum.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116166"},"PeriodicalIF":6.5,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interfacial charge transfer bridge on SrTiO3 crystal boosts solar water splitting","authors":"Xinyi Zhu,&nbsp;Lingling Ding,&nbsp;Ruixue Sun,&nbsp;Jinghan Li,&nbsp;Wenjie Li,&nbsp;Ruize Xu,&nbsp;Lijing Xiang,&nbsp;Fan Fang,&nbsp;Kun Chang","doi":"10.1016/j.jcat.2025.116160","DOIUrl":"10.1016/j.jcat.2025.116160","url":null,"abstract":"<div><div>SrTiO₃ particulate catalysts have demonstrated significant potential in solar water splitting, making them a cost-effective solution for green hydrogen generation. However, the exorbitant total cost associated with utilizing the<!--> <!-->ultra-precious metal Rh even at content as low as 0.1 wt% for hydrogen evolution necessitates the<!--> <!-->exploration of efficient and cost-effective alternatives. In this work, we developed Pt-Ni alloy hydrogen evolution cocatalysts to substitute for Rh. We deposited them with CrO_x passivation layers and CoOOH oxygen evolution cocatalysts onto the surface of the<!--> <!-->K-doped SrTiO₃ crystal for overall water splitting. Studies revealed that K⁺ can serve as an electron accumulation center during photoexcitation and the construction of an<!--> <!-->interfacial K-O-Pt bridge can effectively facilitate the charge transfer. After optimization, Pt₂Ni@CrO_x/K-SrTiO₃/CoOOH exhibits desirable photocatalytic overall water-splitting activity, with the apparent quantum yield (AQY) of 73.46 % (365 nm) and solar-to-hydrogen (STH) conversion efficiency of 0.54 %. This surpasses the catalytic activity of ultra-precious metal Rh and exceeds the catalytic activity of Pt-Ni alloys constructed in situ on Al-SrTiO₃ surfaces. This work would facilitate the development of efficient photocatalysts to produce hydrogen economically.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116160"},"PeriodicalIF":6.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic interfacial and radical strategy enables boosted near-neutral selective photoelectrochemical alcohol oxidation","authors":"Ying Wang ,&nbsp;Deyu Liu ,&nbsp;Weilong Qin ,&nbsp;Yongbo Kuang","doi":"10.1016/j.jcat.2025.116161","DOIUrl":"10.1016/j.jcat.2025.116161","url":null,"abstract":"<div><div>Photoelectrochemical (PEC) systems hold great potential for producing value-added chemicals through the selective oxidation of alcohols in an environmentally friendly manner. However, previous efforts have been hindered by low quantum efficiency, poor selectivity and instability of the photoanodes. To address these issues, we demonstrate the oxidation of benzyl alcohol (BA) into benzaldehyde (BAD) with state-of-the-art efficiency and selectivity using CdS photoanodes incorporated with gold nanoparticles as catalytic sites and sulfites which allow the photoanode to operate through a radical process in near-neutral conditions. This synergistic approach allows the typically vulnerable CdS-based photoanode to maintain PEC Faradaic efficiencies exceeding 95 % for BAD production over 20 h with &gt;99 % selectivity (at pH 9 and 0.6 V versus RHE). The Au-SO₃²⁻ adduct, formed by the strong adsorption of sulfite replacing traditional oxygen/hydroxyl species on the CdS surface, actively catalyzes the selective oxidation of BA. This novel PEC pathway offers a sustainable approach for organic molecule conversion and provides a model for designing efficient PEC processes for solar energy utilization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116161"},"PeriodicalIF":6.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photo/thermo bi-cube mechanism of proton-coupled electron transfer reaction catalyzed by plant light-dependent protochlorophyllide oxidoreductase","authors":"Ruiyuan Liu, Jixian Shang, Zepu Gao, Jing Miao, Yiyi Tian, Xiao Hu, Huizhe Lu","doi":"10.1016/j.jcat.2025.116158","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116158","url":null,"abstract":"Light-dependent protochlorophyllide oxidoreductase (LPOR), one of the few natural light-dependent enzymes relies on the cofactor NADPH to catalyze the conversion of protochlorophyllide to chlorophyllide during chlorophyll biosynthesis. However, acquiring the specific details of LPOR photocatalysis mechanism is challenging, as the intermediate species are generally complex and the chemical steps of interest are often kinetically obscure. Herein, the photochemistry associated with the comprehensive mechanism of C17<img alt=\"double bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/dbnd.gif\" style=\"vertical-align:middle\"/>C18 bond photoreduction inside LPOR was investigated using all-atom molecular dynamics simulations and electronic structure calculations in conjunction with vibronically nonadiabatic proton-coupled electron transfer (PCET) theory. The calculated electronic excitation spectrum and potential energy surfaces demonstrated that the finely modulated optical gap in the LPOR active center facilitates hole-electron separation and intersystem crossing to access the triplet states, which promotes effective photoredox catalysis by LPOR. The electrostatic coupling nature of the charge transfer reactions was revealed by determining the reaction energy paths related to the active site configuration prior to and after the transfer. The entire reaction was ultimately described as hydrogen atom transfer and subsequent stepwise electron and proton transfer process. This work provides a new perspective on the photocatalysis PCET in enzymatic environment with biochemistry relevance.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"17 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"TBD-grafted activated carbon as an efficient solid base catalyst for continuous Knoevenagel reaction","authors":"Yi Chen ,&nbsp;Xueqing Ma ,&nbsp;Chenghao Zhang ,&nbsp;Bingqi Xie ,&nbsp;Wangyang Ma ,&nbsp;Jisong Zhang","doi":"10.1016/j.jcat.2025.116156","DOIUrl":"10.1016/j.jcat.2025.116156","url":null,"abstract":"<div><div>The development of a highly efficient and stable metal-free solid base catalyst for the Knoevenagel reaction remains a significant challenge. In this study, activated carbon is selected as support material to develop a new base catalyst due to its excellent chemical stability. A novel surface chloromethylation method is applied to modify the activated carbon surface, followed by covalent grafting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), resulting in a highly effective solid organic base catalyst. A continuous platform based on a micro-packed bed reactor has been optimized for the Knoevenagel reaction. The system achieves excellent space-time yields (19129.4 <span><math><mrow><msub><mi>g</mi><mrow><mi>P</mi><mi>r</mi><mi>o</mi><mspace></mspace></mrow></msub><msubsup><mrow><mi>k</mi><mi>g</mi></mrow><mrow><mi>c</mi><mi>a</mi><mi>t</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msubsup><mspace></mspace><msup><mrow><mi>h</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup></mrow></math></span>) and demonstrates a broad substrate scope. The solid organic base catalyst exhibits a turnover frequency (<em>TOF</em>) exceeding 140 <span><math><mrow><msup><mrow><mi>h</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup></mrow></math></span>, surpassing the performance of similar nitrogen-based catalysts reported in literature (7.6–68.0 <span><math><mrow><msup><mrow><mi>h</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup></mrow></math></span>). Moreover, the catalyst shows no signs of deactivation after more than 23 h of continuous operation with a turnover number (<em>TON</em>) exceeding 115, indicating comparable performance reported in literature (29.7–297.2). Catalyst deactivation is primarily attributed to the adsorption of raw materials and products onto the base sites, leading to a gradual loss of catalytic activity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116156"},"PeriodicalIF":6.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of zeolite framework on the NO operating cycle in Pd-based passive NOx adsorbers","authors":"Marvi Kaushik ,&nbsp;Tuhin S. Khan ,&nbsp;M. Ali Haider ,&nbsp;Divesh Bhatia","doi":"10.1016/j.jcat.2025.116149","DOIUrl":"10.1016/j.jcat.2025.116149","url":null,"abstract":"<div><div>Density Functional Theory (DFT) simulations are performed to understand the impact of zeolite framework on the operating cycle of NO adsorption and desorption in Pd-based passive NO_x adsorbers. The binding energy on all sites exhibits the trend: BEA &gt; ZSM-5 &gt; CHA, which is consistent with reported trends in the NO_x desorption temperatures. Independent of the zeolite framework, NO binds strongly on Pd¹⁺ site, whereas its binding on Pd(II) sites (Pd²⁺, [PdOH]⁺, dimeric Pd) is considerably weaker. However, the binding strength on Pd¹⁺ and Pd²⁺ sites is similar in ZSM-5 and BEA. The free energy of activation for the reduction of Pd(II) species by NO is dependent on the zeolite framework. NO oxidation on [Pd-O-Pd]²⁺ has a low free energy barrier in ZSM-5 (29 kJ/mol) but exhibits the highest reaction barrier in CHA (77 kJ/mol). Further, the reoxidation of Pd¹⁺ to [Pd-O-Pd]²⁺ is facile in Ferrierite (FER) but has a high free energy barrier in Chabazite (CHA). A kinetic model is developed for Pd/CHA and Pd/BEA which predicts a single desorption peak for CHA and two desorption peaks for BEA. The site-specific NO binding energy trends and the energetics of interconversion between sites result in differences in the NO_x adsorption-desorption characteristics on different zeolite frameworks. The presence of H₂O decreases the NO binding strength on all Pd sites except Pd²⁺ in FER and [PdOH]⁺ in CHA. CO preferentially reduces the Pd(II) species when both CO and NO are co-adsorbed on [PdOH]⁺[PdOH]⁺ with BEA exhibiting the lowest barrier.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116149"},"PeriodicalIF":6.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantified analysis on the conversion from contact electrification to contact-electro-catalysis and the performance of contact-electro-catalysts","authors":"Xuanli Dong,&nbsp;Ziming Wang,&nbsp;Yu Hou,&nbsp;Tingyu Wang,&nbsp;Fu-Jie Lv,&nbsp;Wei Tang","doi":"10.1016/j.jcat.2025.116153","DOIUrl":"10.1016/j.jcat.2025.116153","url":null,"abstract":"<div><div>Contact-electro-catalysis (CEC), utilizing electron transfer during contact electrification (CE) to accelerate chemical reactions, has garnered extensive attention as an emerging field. However, how many activated electrons produced during CE participate in the CEC are necessary to be quantitatively analyzed for further improving the CEC reaction. Hence, we introduce an analytical method for investigating CE-to-CEC conversion at various temperatures and ultrasonic conditions, as well as a quantitative metric of the amount of activated electrons in a single charge transfer cycle for evaluating the performance of different CEC catalysts. This study elucidates the proportion of electrons involved in CEC during CE, which provides insights on the transition from CE to CEC, and facilitates further optimization researches for CEC.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116153"},"PeriodicalIF":6.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advancing electrocatalyst discovery through the lens of data science: State of the art and perspectives","authors":"Xue Jia ,&nbsp;Tianyi Wang ,&nbsp;Di Zhang ,&nbsp;Xuan Wang ,&nbsp;Heng Liu ,&nbsp;Liang Zhang ,&nbsp;Hao Li","doi":"10.1016/j.jcat.2025.116162","DOIUrl":"10.1016/j.jcat.2025.116162","url":null,"abstract":"<div><div>The integration of data science into electrocatalysis has revolutionized the discovery of high-performance catalysts for sustainable energy applications. To emphasize the role of data science and guide future research in electrocatalyst design, this mini-review traces the evolution from low-dimensional data science—rooted in density functional theory (DFT) descriptors such as <em>d</em>-band center and binding/adsorption energies—to high-dimensional analytics powered by large-scale computational datasets and machine learning (ML). First, DFT-derived parameters establish predictive volcano models for various electrochemical reactions, linking atomic-scale descriptors to macroscopic performance within the framework of low-dimensional data science. Meanwhile, with the development of large-scale datasets, ML deciphers complex structure–property relationships, accelerating the design of promising electrocatalysts. Additionally, machine learning potentials (MLPs) bridge quantum precision and scalability, not only accelerating thermodynamic adsorption energy calculations but also enabling simulations of dynamic catalytic mechanisms more efficiently. Finally, we discuss emerging opportunities to deepen data science’s impact. This mini-review highlights the transformative role of data science in bridging theoretical insights, computational efficiency, and experimental validation, ultimately accelerating the design of next-generation electrocatalysts for a sustainable energy future.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116162"},"PeriodicalIF":6.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An efficient catalyst from electrochemical self-reconstruction of NiFePBA/Ni(OH)2 for 5-hydroxymethylfurfural electrooxidation to produce high-valued 2,5-furandicarboxylic acid","authors":"Xuhui Chen ,&nbsp;Hao Liu ,&nbsp;Lei Chen ,&nbsp;Wei Xiong ,&nbsp;Yuqi Liu ,&nbsp;Xiujuan Sun ,&nbsp;Fang Hao","doi":"10.1016/j.jcat.2025.116159","DOIUrl":"10.1016/j.jcat.2025.116159","url":null,"abstract":"<div><div>The utilization of sustainable lignocellulosic biomass for the production of high-value products could potentially solve the intensive reliance on fossil fuels. 2,5-furandicarboxylic acid (FDCA), obtained from 5-hydroxymethylfurfural (HMF) oxidation, is a significant precursor for biomass converted high-value chemicals. Nowadays, the rational design of pre-catalysts <em>via</em> electrochemical self-reconstruction provides an opportunity to design efficient catalysts for electrooxidation process. In this study, we developed a pre-catalyst consisting of nanoscale cubic NiFePBA anchored on Ni(OH)₂. After electrochemical reconstruction, it demonstrated superior HMF oxidation reaction (HMFOR) performance. The results demonstrate that the electrochemical self-reconstruction process converts nanoscale cubic NiFePBA into nanosheeted metal oxyhydroxide, resulting in the formation of an oxygen defect-rich heterostructure with Ni(OH)₂. This reconstruction process also enhance the electrochemically active surface area, thereby increasing the number of active sites. The combined effect of increased active sites and oxygen defects significantly enhances the HMF adsorption and the HMFOR activity. <em>In situ</em> electrochemical impedance spectroscopy further reveals that the reconstructed NiFePBA/Ni(OH)₂-R exhibits accelerated reaction kinetics and reduced reaction potential during the electrocatalytic oxidation of HMF. The NiFePBA/Ni(OH)₂-R catalyst exhibited exceptional electrochemical performance, achieving a high current density of 50 mA·cm^–2 at a relatively low potential of 1.43 V vs. RHE. This performance is characterized by a remarkable 99.1 % conversion of HMF, 98.5 % selectivity for FDCA, and a Faradaic efficiency of 94.2 %. This study offers valuable insights for the development of high-performance HMFOR electrocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116159"},"PeriodicalIF":6.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858130","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}