ChemCatChem最新文献

筛选
英文 中文
Interfacial Engineering to Construct Co3O4/MnO2 Heterostructure for Enhancing the Activity and Stability of Acidic Oxygen Evolution Reaction 构建Co3O4/MnO2异质结构的界面工程提高酸性析氧反应的活性和稳定性
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-24 DOI: 10.1002/cctc.202501068
Shuai Wang, Yiqun Shao, Zhenjie Xie, Xin Yue, Shaoming Huang
{"title":"Interfacial Engineering to Construct Co3O4/MnO2 Heterostructure for Enhancing the Activity and Stability of Acidic Oxygen Evolution Reaction","authors":"Shuai Wang,&nbsp;Yiqun Shao,&nbsp;Zhenjie Xie,&nbsp;Xin Yue,&nbsp;Shaoming Huang","doi":"10.1002/cctc.202501068","DOIUrl":"https://doi.org/10.1002/cctc.202501068","url":null,"abstract":"<p>Designing and developing highly active and stable non-precious metal electrocatalysts for the acidic oxygen evolution reaction (OER) is a key issue in realizing the widespread application of proton exchange membrane water electrolyzers (PEMWEs). Spinel-type Co<sub>3</sub>O<sub>4</sub> has been considered a potential candidate due to its competitive activity for acidic OER; however, its inferior stability hinders its practical deployment. On the other hand, MnO<sub>2</sub> has garnered significant attention due to its excellent resistance to dissolution and self-healing properties in acidic electrolytes. Therefore, we herein report to enhance the activity and stability of acidic OER by interfacial engineering to construct a heterostructure between Co<sub>3</sub>O<sub>4</sub> and MnO<sub>2</sub> (Co<sub>3</sub>O<sub>4</sub>/MnO<sub>2</sub>). As a result, Co<sub>3</sub>O<sub>4</sub>/MnO<sub>2</sub> exhibits efficient activity with a current density of 100 mA cm<sup>−2</sup> at an overpotential of 460 mV and fast kinetics (with a Tafel slope of 62.8 mV dec<sup>−1</sup>) for acidic OER. Meanwhile, the as-prepared heterostructure displays high stability toward acidic OER with maintaining the current density of 10 mA cm<sup>−2</sup> for over 60 h. Detailed characterizations as well as electrochemical in situ spectroscopies reveal that the transfer of electrons across the heterointerfaces enhances the faster lattice-oxygen-mediated mechanism (LOM) pathway, ultimately facilitating the acidic OER process.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 Promoted Hydrogenation of MEA-Captured-CO2 to Methanol 氧空位促进mea捕获的co2加氢制甲醇
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-24 DOI: 10.1002/cctc.202500868
Jiong Sun, Changle Wang, Cuizhen Bai, Dr. Muhammad Kamran, Jiahao Zheng, Zhijing Liang, Prof. Dr. Ruiqin Zhang, Prof. Dr. Songdong Yao, Prof. Dr. Shao-Tao Bai
{"title":"Oxygen Vacancies Promoted Hydrogenation of MEA-Captured-CO2 to Methanol","authors":"Jiong Sun,&nbsp;Changle Wang,&nbsp;Cuizhen Bai,&nbsp;Dr. Muhammad Kamran,&nbsp;Jiahao Zheng,&nbsp;Zhijing Liang,&nbsp;Prof. Dr. Ruiqin Zhang,&nbsp;Prof. Dr. Songdong Yao,&nbsp;Prof. Dr. Shao-Tao Bai","doi":"10.1002/cctc.202500868","DOIUrl":"https://doi.org/10.1002/cctc.202500868","url":null,"abstract":"<p>Integrated CO<sub>2</sub> capture and hydrogenation to methanol is highly likely an economically advantageous technology for flue gas decarbonization and decentralized energy storage. However, highly efficient hydrogenation catalysts are yet to be explored. Herein, we report an efficient metal oxides-carbon-composite supported metal catalyst, Pt/C<sub>SAP</sub>-TiO<sub>2</sub>/CeO<sub>2</sub>, with abundant oxygen vacancies for the highly enhanced hydrogenation of MEA-captured-CO<sub>2</sub> to methanol. An increase in the concentration of oxygen vacancies through catalysts Pt/TiO<sub>2</sub>, Pt/TiO<sub>2</sub>-CeO<sub>2</sub>, and Pt/C<sub>SAP</sub>-TiO<sub>2</sub>/CeO<sub>2</sub> contributes to an improvement in methanol turnovers and yields, as evidenced by x-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), attenuated total reflectance–Fourier-transform infrared spectroscopy (ATR–FTIR), CO<sub>2</sub>-temperature programmed desorption (CO<sub>2</sub>-TPD), O<span> </span>1s X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and catalysis experiments. The optimized supramolecular catalyst Pt/C<sub>SAP</sub>-TiO<sub>2</sub>/CeO<sub>2</sub> exhibited the best activity, with 193% higher TONs than the parent Pt/TiO<sub>2</sub> catalyst (45.3 versus 23.4). A novel supramolecular heterogeneous catalysis mechanism utilizing the surface oxygen vacancies for absorption, preorganization, activation, and conversion of the key challenging formamide intermediate to methanol is proposed.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Sustainable Production of Jet Fuel Additives Through Acetone Self-Condensation Catalyzed by Metal Phosphates 金属磷酸盐催化丙酮自缩合可持续生产喷气燃料添加剂
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-24 DOI: 10.1002/cctc.202500449
Adrián García, Anna Oliva, Pablo Marín, Salvador Ordóñez
{"title":"Sustainable Production of Jet Fuel Additives Through Acetone Self-Condensation Catalyzed by Metal Phosphates","authors":"Adrián García,&nbsp;Anna Oliva,&nbsp;Pablo Marín,&nbsp;Salvador Ordóñez","doi":"10.1002/cctc.202500449","DOIUrl":"https://doi.org/10.1002/cctc.202500449","url":null,"abstract":"<p>Acetone is a promising platform molecule for renewable processes, as it can be obtained from biomass via fermentation or pyrolysis. In the presence of acid or base catalysts, acetone condenses and dehydrates, leading to the formation of mesitylene. A sustainable production process using renewable sources is needed to meet the demand for mesitylene, a compound with applications in the chemical and pharmaceutical industries, as well as in aviation fuel additive. The work explores the potential of Ti and Al phosphates as acid catalysts for the gas-phase self-condensation of acetone to mesitylene. These materials were synthesized by simple one-pot evaporation induced self-assembly method and precipitation. The Ti phosphate was modified with K and Si to tailor acid-sites distribution. Catalytic activity and stability were studied in a fixed-bed continuous reactor at 225 °C, space velocity of 1900 mol/(kg h)) and a feed of 15% acetone in nitrogen. Fresh and used catalysts were characterized to determine the structure–reactivity relationships. In this context, the presence of mild and strong Brønsted acid sites was correlated to a higher deactivation by strong adsorption of high-molecular-weight condensation products.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500449","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Merging Iron Catalysis and Enzymatic Reduction: A Deracemization Strategy of Secondary Alcohols in Iron-Based Deep Eutectic Solvents 合并铁催化和酶还原:仲醇在铁基深共晶溶剂中的离消旋策略
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-24 DOI: 10.1002/cctc.202501019
Dr. Mara Pulpito, Dr. Luciana Cicco, Prof. Filippo Maria Perna, Prof. Paola Vitale, Prof. Vito Capriati, Prof. Vicente Gotor-Fernández
{"title":"Merging Iron Catalysis and Enzymatic Reduction: A Deracemization Strategy of Secondary Alcohols in Iron-Based Deep Eutectic Solvents","authors":"Dr. Mara Pulpito,&nbsp;Dr. Luciana Cicco,&nbsp;Prof. Filippo Maria Perna,&nbsp;Prof. Paola Vitale,&nbsp;Prof. Vito Capriati,&nbsp;Prof. Vicente Gotor-Fernández","doi":"10.1002/cctc.202501019","DOIUrl":"https://doi.org/10.1002/cctc.202501019","url":null,"abstract":"<p>The use of deep eutectic solvents (DESs) has gained increasing attention over the past two decades as green (co)solvents for performing organic reactions and biotransformations under mild conditions. In this study, we report a deracemization strategy that highlights the potential of FeCl<sub>3</sub>·6H<sub>2</sub>O/urea (2:1 mol/mol) as a task-specific DES. This neoteric solvent not only enhances substrate solubility but also plays a crucial role in the oxidation step of various racemic alcohols. The chemoenzymatic process consists of two consecutive sequential redox steps, starting with an initial non-selective oxidation of the hydroxyl group using TEMPO in the FeCl<sub>3</sub>·6H<sub>2</sub>O/urea medium, followed by a stereoselective bioreduction of the resulting carbonyl intermediate. Notably, the use of stereocomplementary alcohol dehydrogenases (ADHs)—namely ADH-A (Prelog selectivity), <i>Lb</i>ADH, and evo 1.1.200 (anti-Prelog selectivity)—is shown to be compatible with the DES system, enabling the efficient conversion of racemic alcohols into enantiomerically enriched products. Enantiomeric excesses of up to &gt;99% were achieved, demonstrating the effectiveness of this DES-based chemoenzymatic platform in producing optically active alcohols from racemic mixtures.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202501019","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317734","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
H2 Activation and Adsorbed H Species on Pt-Based Heterogeneous Catalysts: Fundamentals and Advances pt基非均相催化剂上H2活化及吸附氢的研究进展
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-22 DOI: 10.1002/cctc.202500902
Qiangqiang Wu, Weixiang Xiong, Guangxing Yang
{"title":"H2 Activation and Adsorbed H Species on Pt-Based Heterogeneous Catalysts: Fundamentals and Advances","authors":"Qiangqiang Wu,&nbsp;Weixiang Xiong,&nbsp;Guangxing Yang","doi":"10.1002/cctc.202500902","DOIUrl":"10.1002/cctc.202500902","url":null,"abstract":"<p>H<sub>2</sub> activation on heterogeneous catalysts is a fundamental step in numerous chemical processes, with the nature of adsorbed hydrogen (H) species playing a critical role in catalytic performance. In this review, we systematically categorize the formation of different H species based on the coordination environment of active metal sites, distinguishing between homolytic and heterolytic H<sub>2</sub> dissociation pathways. Focusing on Pt-based heterogeneous catalysts, we provide atomic-scale insights into adsorbed H species and Pt metal. The experimental detection of Pt─H adducts is then critically evaluated via three key spectroscopic techniques: infrared (IR) spectroscopy, inelastic neutron scattering (INS) spectroscopy, and X-ray absorption spectroscopy (XAS), highlighting recent advancements in spectral interpretation. Complementary theoretical studies that can provide binding details of Pt─H bonds are also discussed to elucidate Pt─H adsorption configurations, binding energies, dynamic properties, and coverage-dependent behavior. Finally, we summarize the strengths and limitations of each characterization method and provide perspectives on future research directions for understanding adsorbed H species in catalysis. This review aims to bridge the gap between experimental observations and theoretical modeling, offering a comprehensive foundation for designing more efficient catalysts in hydrogen-involved reactions.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145101962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Ribosomal Incorporation of Thioxanthone as a Noncanonical Amino Acid Facilitates the Engineering of Photoenzymes 硫氧蒽酮作为非规范氨基酸的核糖体整合促进了光酶的工程
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-19 DOI: 10.1002/cctc.202500847
Marco Seifert, Dr. Martin Termathe, Dr. Luca Nardo, Prof. Dr. Matthias Höhne
{"title":"Ribosomal Incorporation of Thioxanthone as a Noncanonical Amino Acid Facilitates the Engineering of Photoenzymes","authors":"Marco Seifert,&nbsp;Dr. Martin Termathe,&nbsp;Dr. Luca Nardo,&nbsp;Prof. Dr. Matthias Höhne","doi":"10.1002/cctc.202500847","DOIUrl":"https://doi.org/10.1002/cctc.202500847","url":null,"abstract":"<p>Photocatalysis in biocatalytic systems provides a promising approach for achieving selective and efficient chemical transformations under mild conditions. Naturally occurring photoactive cofactors are rare. To overcome this limitation, genetic code engineering can be applied to equip proteins with additional functionalities beyond those known in the 20 canonical amino acids. Here, we report the engineering of an aminoacyl-tRNA synthetase (thioXRS) that allows the incorporation of a thioxanthone-bearing noncanonical amino acid (thioX). As proof-of-concept, we utilized the versatile biocatalyst LmrR as a protein scaffold. We identified an active variant able to catalyze the <i>E</i>/<i>Z</i>-photoisomerization of a cinnamate ester derivative into coumarin. The reaction design allows direct monitoring through fluorescence measurements, as the fluorescent substrate is converted into a non-fluorescent product. This work demonstrates that thioXRS is a versatile tool for the future development of new-to-nature photoenzymes, expanding the synthetic capabilities of biocatalysis towards light-driven transformations.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500847","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Carbon Dioxide and Epoxide Copolymerization Processes: Advances in Catalyst Design Over Decades 二氧化碳和环氧化物共聚工艺:几十年来催化剂设计的进展
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-19 DOI: 10.1002/cctc.202500959
Ishtiyaq Ahmad Wani, Mohsin Hassan, Gulzar A. Bhat
{"title":"Carbon Dioxide and Epoxide Copolymerization Processes: Advances in Catalyst Design Over Decades","authors":"Ishtiyaq Ahmad Wani,&nbsp;Mohsin Hassan,&nbsp;Gulzar A. Bhat","doi":"10.1002/cctc.202500959","DOIUrl":"https://doi.org/10.1002/cctc.202500959","url":null,"abstract":"<p>The selective synthesis of polycarbonates (PCs) or cyclic carbonates via catalytic conversion of epoxides and carbon dioxide (CO<sub>2</sub>) is an efficient pathway for producing valuable products from CO<sub>2</sub>. This approach has received significant attention because it offers control over mechanical, thermal, and degradable characteristics of the resulting PCs. However, activating CO<sub>2</sub> as a C1-feedstock in such reactions is a challenging task owing to the considerable thermodynamic stability of CO<sub>2</sub>. Therefore, the use of catalysts along with precise temperature and pressure control is essential for successful CO<sub>2</sub> copolymerization with cyclic ethers. Since Inoue and co-workers pioneering discovery of zinc-based catalysts for these reactions in 1969, substantial advancements have been made for understanding the mechanisms of these catalytic systems. These developments have led to the synthesis of more efficient catalytic systems that can operate under ambient conditions and allow selective epoxides/CO<sub>2</sub> copolymerization. Metal-based catalytic systems, particularly those utilizing Zn, Co, Cr, and Al have dominated this field, while recent reports highlight the potential of metal-free organocatalytic systems. Alongside specific catalytic frameworks, many novel molecules have been introduced into the catalytic toolbox. This review will summarize recent developments in exploring novel catalysts for the catalytic conversion of CO<sub>2</sub> and epoxides into aliphatic polycarbonates.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Dual-Acid Mesostructured Cellular Foams (SO3H and Mo) as Efficient Catalysts for Dibenzothiophene Oxidation 双酸介结构泡沫(SO3H和Mo)作为二苯并噻吩氧化的高效催化剂
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-19 DOI: 10.1002/cctc.202500747
Dr. Ardian Nurwita, Dr. Katarzyna Stawicka, Dr. Anna Wojtaszek-Gurdak, Prof. Dr. Maciej Trejda
{"title":"Dual-Acid Mesostructured Cellular Foams (SO3H and Mo) as Efficient Catalysts for Dibenzothiophene Oxidation","authors":"Dr. Ardian Nurwita,&nbsp;Dr. Katarzyna Stawicka,&nbsp;Dr. Anna Wojtaszek-Gurdak,&nbsp;Prof. Dr. Maciej Trejda","doi":"10.1002/cctc.202500747","DOIUrl":"https://doi.org/10.1002/cctc.202500747","url":null,"abstract":"<p>Mesostructured cellular foam (MCF) materials were modified with sulfonic acid (TPS) and molybdenum species to obtain dual-site catalysts containing both Brønsted and Lewis acid sites. The physicochemical properties of the materials were characterized using N<sub>2</sub> adsorption–desorption, XRD, SEM-EDX, XPS, pyridine adsorption combined with FT-IR and UV–vis spectroscopy. N<sub>2</sub> physisorption revealed that TPS and molybdenum incorporation led to pore blockage and surface area reduction, particularly for Mo/MCF. XRD and SEM-EDX analyses indicated that molybdenum species are well dispersed, although TPS presence promoted localized accumulation, suggesting interactions between the two components. The catalysts were evaluated in dibenzothiophene (DBT) oxidation using H<sub>2</sub>O<sub>2</sub>. Mo/TPS/MCF exhibited superior activity, achieving 100% DBT conversion within 30 min at 80 °C, outperforming TPS/MCF and Mo/MCF. Moreover, the dual-site catalyst maintained high activity over five consecutive cycles, whereas Mo/MCF showed significant deactivation due to molybdenum leaching. These results demonstrate that TPS plays a stabilizing role for molybdenum species and enhances catalytic performance. The interaction between Brønsted and Lewis acid sites in Mo/TPS/MCF offers a promising strategy for efficient and recyclable oxidative desulfurization catalysts.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
Electronic Effects of Al Doping on the Mechanism of Methanol Formation on an Al Doped Cu/ZnO Interface Model Al掺杂对Al掺杂Cu/ZnO界面模型甲醇形成机理的电子效应
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202500824
David A. Jurado A., Michael D. Higham, C. Richard A. Catlow, Ingo Krossing
{"title":"Electronic Effects of Al Doping on the Mechanism of Methanol Formation on an Al Doped Cu/ZnO Interface Model","authors":"David A. Jurado A.,&nbsp;Michael D. Higham,&nbsp;C. Richard A. Catlow,&nbsp;Ingo Krossing","doi":"10.1002/cctc.202500824","DOIUrl":"https://doi.org/10.1002/cctc.202500824","url":null,"abstract":"<p>The mechanism of CO<sub>2</sub> hydrogenation to methanol is modelled using plane-wave DFT applied to a representative Cu<sub>8</sub>-ZnO(CZ) model, reported previously, with aluminium substituting a bulk Zn (= Cu/ZnO/Al<sub>2</sub>O<sub>3</sub>(CZA)). On CZA, CO<sub>2</sub> adsorption and activation are enhanced at the active Cu/ZnO interface compared to systems with a Cu-based or CZ-based interface, demonstrating Al's electronic effect. Methanol formation at CZA follows the formate path: <b>CO<sub>2</sub>*→ HCOO*→ H<sub>2</sub>COO*→ H<sub>2</sub>COOH*→ H<sub>2</sub>CO*→ H<sub>2</sub>COH*→ H<sub>3</sub>COH</b>, with small contributions from the RWGS mechanism. Methoxy's binding is enhanced, making it a dead-end and not an intermediate as on CZ. Formate intermediate at the Cu/Zn interface in CZA is electronically destabilized through Al. By contrast, other surface formates are stabilized and act as spectators. The most energy demanding step is the hydrogenation of formate to dioxomethylene (<i>E</i><sub>a</sub> = 1.08 eV) and not methoxy hydrogenation as on CZ. Multiple species are able to scavenge O* regenerating the active interfacial site. OH* was found to poison the active site, although its formation is energy demanding, making the CZA system overall more selective to MeOH than CZ. Water formation occurs on the Cu site as on the CZ system, although Zn sites can stabilize adsorbed water consistent to on experiments at CZA.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500824","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Nanoporous Cobalt-Doped Fe3P for Boosted Electrochemical Nitrate Reduction 纳米多孔钴掺杂Fe3P促进硝酸盐电化学还原
IF 3.9 3区 化学
ChemCatChem Pub Date : 2025-08-15 DOI: 10.1002/cctc.202501002
Xiechen Zhang, Yanqin Liang, Hui Jiang, Zhaoyang Li, Zhonghui Gao, Shuilin Wu, Zhenduo Cui, Shengli Zhu, Wence Xu
{"title":"Nanoporous Cobalt-Doped Fe3P for Boosted Electrochemical Nitrate Reduction","authors":"Xiechen Zhang,&nbsp;Yanqin Liang,&nbsp;Hui Jiang,&nbsp;Zhaoyang Li,&nbsp;Zhonghui Gao,&nbsp;Shuilin Wu,&nbsp;Zhenduo Cui,&nbsp;Shengli Zhu,&nbsp;Wence Xu","doi":"10.1002/cctc.202501002","DOIUrl":"https://doi.org/10.1002/cctc.202501002","url":null,"abstract":"<p>Electrocatalytic nitrate reduction reaction (NO<sub>3</sub>RR) offers a sustainable avenue for mitigating nitrate pollution and enabling decentralized ammonia production. However, achieving high efficiency and selectivity remains challenging due to the sluggish multielectron transfer kinetics. Herein, we report a nanoporous Co-Fe<sub>3</sub>P catalyst featuring cobalt-doped iron phosphide frameworks that modulate the d band center, thereby optimizing intermediate binding and enhancing catalytic performance. The catalyst delivers a high ammonia yield rate of 24.56 mg h<sup>−1</sup> cm<sup>−</sup><sup>2</sup> and a Faradaic efficiency of 91.45% at −0.4 V versus reversible hydrogen electrode (RHE) in alkaline media. In situ infrared spectroscopy identifies key intermediates, such as NH<sub>2</sub>OH, NO<sub>2</sub><sup>−</sup>, and NH<sub>2</sub>, indicative of an associative pathway. Furthermore, when integrated into a Zn–NO<sub>3</sub><sup>−</sup> battery, the Co-Fe<sub>3</sub>P cathode enables a high-power density of 15.83 mW cm<sup>−</sup><sup>2</sup> with excellent Faradaic efficiency and cycling stability.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
相关产品
×
本文献相关产品
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信