ACS Chemical Biology最新文献

{"title":"Unique Electron Donor–Acceptor Complex Conformation Ensures Both the Efficiency and Enantioselectivity of Photoinduced Radical Cyclization in a Non-natural Photoenzyme","authors":"Matteo Capone,&nbsp;Gianluca Dell’Orletta,&nbsp;Claire G. Page,&nbsp;Todd K. Hyster,&nbsp;Gregory D. Scholes and Isabella Daidone*,&nbsp;","doi":"10.1021/acscatal.4c0504610.1021/acscatal.4c05046","DOIUrl":"https://doi.org/10.1021/acscatal.4c05046https://doi.org/10.1021/acscatal.4c05046","url":null,"abstract":"<p >Non-natural photoenzymatic catalysis exploits active site tunability for stereoselective radical reactions. In flavoproteins, light absorption promotes the excitation of an electron donor–acceptor (EDA) complex formed between the reduced flavin cofactor and a substrate (α-chloroacetamide in this case). This can trigger chloride mesolytic cleavage, leading to radical cyclization (forming a γ-lactam), or revert to the ground state. While this strategy is feasible using a broad UV/visible/near-infrared spectrum, the low quantum yield presents a significant challenge. Using a multiscale computational approach, we elucidate the mechanisms of the light-driven radical initiation step catalyzed by a Gluconobacter oxydans “ene”-reductase mutant (GluER-G6). The low experimental quantum yield stems from the limited population (&lt;10%) of EDA complexes with a charge transfer state competent for mesolytic cleavage. Accessibility of this state requires substrate bending positioning the chlorine atom near the styrenic group. A subset of these reactive conformers exhibits enhanced cyan/red absorption due to the optimal C–Cl bond alignment with the flavin. Engineering a GluER variant to stabilize this conformation is expected to significantly enhance catalytic efficiency when using cyan/red light. The identified reactive intermediates possess the correct prochirality for enantioselective cyclization. Our findings show that ground-state conformational selection of these EDA complex conformers governs both light-activated mesolytic cleavage and enantioselectivity.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16488–16496 16488–16496"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tetrahydroxybenzoquinone-Based Two-Dimensional Conductive Metal–Organic Framework via π-d Conjugation Modulation for Enhanced Oxygen Evolution Reaction","authors":"Yantao Wang,&nbsp;Xiaowan Bai,&nbsp;Junfeng Huang,&nbsp;Wangzu Li,&nbsp;Jinhua Zhang,&nbsp;Hua Li,&nbsp;Yu Long,&nbsp;Yong Peng* and Cailing Xu*,&nbsp;","doi":"10.1021/acscatal.4c0497710.1021/acscatal.4c04977","DOIUrl":"https://doi.org/10.1021/acscatal.4c04977https://doi.org/10.1021/acscatal.4c04977","url":null,"abstract":"<p >2D conductive metal–organic frameworks (2D c-MOFs) have attracted significant interest as efficient electrocatalysts for the oxygen evolution reaction (OER). However, effectively regulating their catalytic activity remains a significant challenge. Herein, density functional theory (DFT) was performed to explore the effect of π-d conjugation modulation on the electronic structure of the tetrahydroxy-1,4-benzoquinone-based 2D c-MOFs. The computational results indicate that the strong π-d conjugation caused by orbital hybridization between Co and Fe widens and enhances the hybridization between the d_<i>xz</i>/d_<i>yz</i> orbitals at the metal sites and the p orbitals of the ligands, thereby affecting the reconstruction of the MOFs during the OER process. Experimentally, CoFe-THQ with various atomic ratios was synthesized. The results indicated that the synthesized Co_0.6Fe_0.4-THQ powders only needs an overpotential of 247 mV to reach a current density of 10 mA cm^–2 for the OER in alkaline medium, which is much lower than most reported transition metal-based electrocatalysts and even better than that of the benchmark RuO₂ electrocatalyst. Furthermore, in situ Raman and in situ Fourier transform infrared spectroscopy analyses revealed that Co_0.6Fe_0.4-THQ undergoes a different reconstruction evolution during the OER process compared to Co-THQ, with the mixed (Co, Fe) bimetallic oxides ((Co, Fe)₃O₄ and α-(Co, Fe)₂O₃) formed after reconstruction identified as the true active species. This study opens up an effective avenue for the rational design of high-activity 2D c-MOF electrocatalysts.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16532–16542 16532–16542"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Epoxy Group Modified Atomic Zn–N2O2 for H2O2 Electrosynthesis and Sulfide Oxidation","authors":"Chengbo Ma,&nbsp;Jun Wang,&nbsp;Xiaomei Liu,&nbsp;Ning Li,&nbsp;Wen Liu,&nbsp;Yang Li,&nbsp;Xiaobin Fan and Wenchao Peng*,&nbsp;","doi":"10.1021/acscatal.4c0472910.1021/acscatal.4c04729","DOIUrl":"https://doi.org/10.1021/acscatal.4c04729https://doi.org/10.1021/acscatal.4c04729","url":null,"abstract":"<p >In this study, zinc single-atom catalysts (SACs) (Zn SACs) with Zn–N₂O₂ as the coordination shell and the epoxy group (C–O–C) as the second coordination structure are synthesized. The obtained Zn SACs exhibit a high 2e^– ORR selectivity of &gt;85% in a wide potential window of 0–0.65 V vs RHE and achieve a high generation rate of 828.9 mmol g_cat^–1 h^–1 for H₂O₂. Experimental and theoretical calculations have confirmed that the second coordination structure of adjacent C–O–C can effectively optimize the adsorption energy of Zn–N₂O₂ for *OOH and tune the 2e^– ORR selectivity. In addition, a small onset potential of 0.38 V vs RHE is achieved for sulfides oxidation reaction (SOR) by the obtained Zn SACs. Moreover, a coupled system of anodic SOR and cathodic 2e^– ORR is fabricated, which can save 45% energy consumption compared to the OER-2e^– ORR system due to a decreased cell voltage of 2.03 V at 20 mA cm^–2. This study provides new bifunctional Zn SACs modified by adjacent C–O–C, which are effective as bifunctional catalysts for electrosynthesis of H₂O₂ and electro-oxidation of sulfides. These two reactions can be performed together in a coupled system with decreased energy cost and thus should have better application potential.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16522–16531 16522–16531"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis","authors":"Fuyuan Li,&nbsp;Fa-Yu Liu,&nbsp;Xiaowei Zhao*,&nbsp;Yanli Yin,&nbsp;Bin Yu,&nbsp;Junmin Zhang* and Zhiyong Jiang*,&nbsp;","doi":"10.1021/acscatal.4c0463810.1021/acscatal.4c04638","DOIUrl":"https://doi.org/10.1021/acscatal.4c04638https://doi.org/10.1021/acscatal.4c04638","url":null,"abstract":"<p >In contemporary organic synthesis, chemists actively pursue a diverse range of substrates that can be efficiently catalyzed within an integrated system, playing a crucial role in advancing the pharmaceutical industry. However, due to the influence of substituents on reactivity and selectivity, it poses a challenging dilemma to explore different strategies for activating substrates with distinct functional groups. Herein, we have developed an important visible light-driven chiral Lewis acid catalysis platform which facilitates the unified allylations and vinylogous reactions of various allyl bromides and isatins for the highly enantio- and diastereoselective construction of valuable 3-allyl-3-hydroxy oxindoles. The success of this approach lies in utilizing a radical pathway for intermediate formation and stereocenter generation. Moreover, the activation capability of chiral Lewis acids provides an opportunity to achieve sufficient enantiocontrol and enhance regioselectivity. The robustness of this method is demonstrated by its application in precise radical-based propargylation reactions using readily accessible propargyl bromides.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16479–16487 16479–16487"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Functional Nucleic Acid Enzymes: Nucleic Acid-Based Catalytic Factories","authors":"Min Yang,&nbsp;Yushi Xie,&nbsp;Longjiao Zhu,&nbsp;Xiangyang Li and Wentao Xu*,&nbsp;","doi":"10.1021/acscatal.4c0267010.1021/acscatal.4c02670","DOIUrl":"https://doi.org/10.1021/acscatal.4c02670https://doi.org/10.1021/acscatal.4c02670","url":null,"abstract":"<p >Biocatalysis plays a vital role in the operations of all living organisms, which is usually thought to be mediated by protein enzymes. However, the pioneering discovery of self-splicing intron-splicing RNA ribozyme demonstrated that nucleic acids can also promote catalysis, with efficiency comparable to that of proteases. The discovery of deoxyribozyme (DNAzymes) further broadened the understanding of the catalytic function of nucleic acids. Since then, nucleic acids with various catalytic functions have been gradually discovered and significant efforts have been devoted to the applications studies of nucleic acid catalyst. Consequently, a systematically and comprehensive review is needed to summarize all the advancements in the FNAzymes field. In this review, we propose the concept of functional nucleic acid enzymes (FNAzymes). FNAzymes are nucleic acids or nucleic acid complexes with special structure and catalytic functions. Then FNAzymes are divided into four groups based on the components that make them up: ribozymes, DNAzymes, modified FNAzymes, and functional nucleic acid nanozymes (FNA nanozymes). In addition, the catalytic function, structure, and catalytic mechanism of each FNAzymes are introduced. The applications of FNAzymes in biosensing, bioimaging, and biotherapy of are summarized. Finally, future development trends and application prospects of functional nucleases are discussed.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16392–16422 16392–16422"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boosting Low-Temperature CO2 Methanation Activity on Ru/Anatase-TiO2 Via Mn Doping: Revealing the Crucial Role of CO2 Dissociation","authors":"Shaorong Deng,&nbsp;Zijian Qian,&nbsp;Chenji Zhu,&nbsp;Boxing Cheng,&nbsp;Xiaowei Wang,&nbsp;Xiuzhong Fang,&nbsp;Xianglan Xu* and Xiang Wang,&nbsp;","doi":"10.1021/acscatal.4c0380110.1021/acscatal.4c03801","DOIUrl":"https://doi.org/10.1021/acscatal.4c03801https://doi.org/10.1021/acscatal.4c03801","url":null,"abstract":"<p >A series of Ru/Ti_1–<i>x</i>Mn_<i>x</i>O₂ catalysts with varying Mn/(Ti + Mn) molar ratios (<i>x</i> = 0.10–0.25) were synthesized to investigate the CO₂ methanation mechanism on anatase TiO₂-supported Ru catalysts (Ru/a-TiO₂) and develop high-performance catalysts at low temperatures. Among these catalysts, the Ru/Ti_0.8Mn_0.2O₂ exhibited the highest activity, achieving approximately 65% CO₂ conversion at 230 °C, which is markedly superior to the unmodified Ru/a-TiO₂ catalyst yielding only about 15% CO₂ conversion. The majority of Mn cations were incorporated into the lattice of a-TiO₂ as Mn³⁺ cations, forming a solid solution structure in the Ti_0.8Mn_0.2O₂ support. This modification resulted in a higher specific surface area, improved reducibility, and increased oxygen vacancy compared with pure a-TiO₂. Consequently, Ru dispersion and electronic metal–support interactions were enhanced in Ru/Ti_0.8Mn_0.2O₂ compared to those in Ru/a-TiO₂. In-situ diffuse reflectance infrared Fourier transform spectroscopy combined with temperature-programmed surface reaction experiments revealed that CO₂ methanation predominantly proceeded via the CO* route on the Ru/a-TiO₂. The CO₂ adsorption in the presence of decomposed H₂ led to dissociation to linear CO*, followed by CO methanation where CO₂ dissociation to CO* was identified as the rate-determining step (RDS). Mn cation doping induced the formation of oxygen vacancies, significantly enhancing CO₂ dissociation on Ru/Ti_0.8Mn_0.2O₂, thereby shifting the RDS to CO methanation. This mechanism explains the superior activity of Ru/Ti_0.8Mn_0.2O₂ at low temperatures for CO₂ methanation compared to the Ru/a-TiO₂.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16508–16521 16508–16521"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modulating CO2 Electroreduction Activity on Mo2C and Promoting C2 Product by Grain Boundary Engineering: Insights from First-Principles Calculations","authors":"Yuxing Lin,&nbsp;Fangqi Yu,&nbsp;Lei Li,&nbsp;Yameng Li,&nbsp;Rao Huang and Yuhua Wen*,&nbsp;","doi":"10.1021/acscatal.4c0320210.1021/acscatal.4c03202","DOIUrl":"https://doi.org/10.1021/acscatal.4c03202https://doi.org/10.1021/acscatal.4c03202","url":null,"abstract":"<p >Recently, two-dimensional transition-metal carbides and/or nitrides (MXenes) have attracted extensive interest owing to their promising applications in electrochemistry, especially in electrocatalysis for the CO₂ reduction reaction (CO₂RR). However, there still exist challenges in developing MXene electrocatalysts with high activity and selectivity. Grain boundaries (GBs) could potentially provide active sites for chemical reactions, and their existence may be helpful for improving various electrocatalytic performances of MXenes. In this work, we constructed nine types of GBs in the Mo₂C monolayer and employed density functional theory (DFT) calculations to systematically investigate their effects on the conversion efficiency of CO₂ and the diversity of CO₂RR products. Our study reveals that the presence of different valence states of Mo atoms at the GBs breaks the symmetry of CO₂ adsorption on Mo₂C, which promotes the activation of CO₂ and diversifies the CO₂RR products. Especially, these GBs exhibited remarkably low limiting potentials for C₁ products, e.g., −0.29 V for CH₄ on 5|7c GB, −0.31 V for CH₃OH on 4|8 GB, and −0.55 V for HCOOH on 4|4a GB. Furthermore, the reduced potential barriers at the GBs, such as 0.26 eV for 5|7b GB and 0.13 eV for 8|8b GB, facilitate the C–C coupling and promote the formation of C₂ products. These findings demonstrate that the introduction of GBs can enhance both the electrocatalytic activity of Mo₂C for the CO₂RR and the diversity of CO₂RR products, therefore paving the way for designing and advancing high-efficiency MXene electrocatalysts through GB engineering.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16423–16433 16423–16433"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reaction Mechanisms and Applications of Single Atom Catalysts for Thermal-Catalytic Carbon Dioxide Hydrogenation Toward Oxygenates","authors":"Fei Wang,&nbsp;Yicheng Liu,&nbsp;Mengke Peng,&nbsp;Mengyao Yang,&nbsp;Yuanyuan Chen,&nbsp;Juan Du* and Aibing Chen*,&nbsp;","doi":"10.1021/acscatal.4c0606510.1021/acscatal.4c06065","DOIUrl":"https://doi.org/10.1021/acscatal.4c06065https://doi.org/10.1021/acscatal.4c06065","url":null,"abstract":"<p >Thermo-catalytic CO₂ hydrogenation to high-value oxygenates has been regarded as one of the most powerful strategies that can potentially alleviate excessive CO₂ emissions. However, due to the high chemical stability of CO₂ and the variability of hydrogenation pathways, it is still challenging to achieve highly active and selective CO₂ hydrogenation. Single atom catalysts (SACs) with ultrahigh metal utilization efficiency and extraordinary electronic features have displayed growing importance for thermo-catalytic CO₂ hydrogenation with multiple strategies developed to improve performances. Here, we review breakthroughs in developing SACs for efficient CO₂ hydrogenation toward common oxygenates (CO, HCOOH, CH₃OH, and CH₃CH₂OH) in the following order: first, an analysis of reaction mechanisms and thermodynamics challenges of CO₂ hydrogenation reactions; second, a summary of metal SAs designed by dividing them into the two categories of the single- and dual-sites; third, discussion of support effects with a focus on approaches to regulating strong metal–support interaction (MSI). Summarily, current challenges and future perspectives to develop higher-performance SACs in CO₂ hydrogenation are presented. We expect that this review can bring more design inspiration to trigger innovation in catalytic CO₂ evolution materials and eventually benefit the achievement of the carbon-neutrality goal.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16434–16458 16434–16458"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Variable Mechanisms for Cobalt-Catalyzed Alkyne Dimerization Pinpointed by Quasi-Classical Trajectory Simulations","authors":"Haohua Chen,&nbsp;Zhile Dang,&nbsp;Xiantong Sha,&nbsp;Yu Wang,&nbsp;Zhiguo Zhang,&nbsp;Yixin Luo* and Yu Lan*,&nbsp;","doi":"10.1021/acscatal.4c0374910.1021/acscatal.4c03749","DOIUrl":"https://doi.org/10.1021/acscatal.4c03749https://doi.org/10.1021/acscatal.4c03749","url":null,"abstract":"<p >Transition metal-catalyzed alkyne dimerization represents a powerful method for the construction of enynes. However, the ambiguous hydrogen transfer mechanism during the dimerization has resulted in controlling the regio-, stereo-, and, where applicable, chemoselectivity remaining a long-standing challenge. Herein, a combination of DFT calculations and quasi-classical MD simulations was used to interrogate the dynamic motion of hydrogen in cobalt-catalyzed alkyne dimerization. The collective results inspired us to propose, for the first time, a substrate-dependent differential hydride transfer model involving either concerted oxidative hydrogen transfer or stepwise oxidative addition, followed by alkyne insertion. The practicability and universality of this oxidative hydride transfer mechanism were further validated by the theoretical studies of experimentally observed selective cross- and homo-dimerization. Charge distribution analyses depicted that the differentiation between those two hydride transfer mechanisms originates from the α-silicon effect, which can stabilize the neighboring negative charge of the alkyne. Furthermore, a comprehensive DFT study of the substituent effects of alkynes reveals that the electron-withdrawing group will accelerate the oxidative hydride transfer process, which can open up avenues for mechanistic-oriented selective dimerization.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16469–16478 16469–16478"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Role of High-Valence Metal Dissolution in Oxygen Evolution Kinetics of the Advanced FeNiOx Catalysts","authors":"Jun Ke,&nbsp;Jiaxi Zhang*,&nbsp;Longhai Zhang,&nbsp;Shunyi He,&nbsp;Chengzhi Zhong,&nbsp;Li Du,&nbsp;Huiyu Song,&nbsp;Xiaoming Fang*,&nbsp;Zhengguo Zhang and Zhiming Cui*,&nbsp;","doi":"10.1021/acscatal.4c0445410.1021/acscatal.4c04454","DOIUrl":"https://doi.org/10.1021/acscatal.4c04454https://doi.org/10.1021/acscatal.4c04454","url":null,"abstract":"<p >The incorporation of high-valence metals into FeNi-based oxides has been widely accepted as an efficient approach for facilitating the alkaline oxygen evolution reaction (OER), but the corresponding structure–property relationship remains unclear due to the lack of identification of the real structure. In this study, we reveal the surface evolution processes of M-doped FeNi oxides (M is Mo, V, and W) and elucidate the role of M dissolution in enhancing oxygen evolution kinetics. Taking Mo as an example, the high-valence metal Mo was doped into FeNiO_<i>x</i> and its leaching behavior was observed during OER. By combining in situ Raman analysis, electrochemical measurement, and first-principles calculation, it was unveiled that the electro-dissolution of Mo, in the form of MoO₄^2–, led to preferential removal of lattice oxygen, thereby facilitating the adsorption step of OH and triggering the lattice oxygen-mediated mechanism for promoting OER. Consequently, the optimized FeNiMoO_<i>x</i> displayed an overpotential of only 235 mV to reach 10 mA/cm² and a 30-fold enhancement in specific activity compared with that of FeNiO_<i>x</i> at 1.53 V. Our findings provide a different perspective on the intricate association between dissolution of high-valence metal and alkaline OER performance, elucidating the key role of the dissolution-induced structure change on promoting the OER mechanism.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16363–16373 16363–16373"},"PeriodicalIF":11.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}