ACS Catalysis 最新文献

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Surface Engineering on Ag-Decorated Co3O4 Electrocatalysts for Boosting Nitrate Reduction to Ammonia 促进硝酸盐还原成氨的 Ag-Decorated Co3O4 电催化剂的表面工程技术
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-12 DOI: 10.1021/acscatal.4c01510
Ming Zhang, Zhipeng Ma, Shujie Zhou, Chen Han, Varun Kundi, Priyank V. Kumar, Lars Thomsen, Bernt Johannessen, Lingyi Peng, Yihao Shan, Constantine Tsounis, Yuwei Yang, Jian Pan, Rose Amal
{"title":"Surface Engineering on Ag-Decorated Co3O4 Electrocatalysts for Boosting Nitrate Reduction to Ammonia","authors":"Ming Zhang, Zhipeng Ma, Shujie Zhou, Chen Han, Varun Kundi, Priyank V. Kumar, Lars Thomsen, Bernt Johannessen, Lingyi Peng, Yihao Shan, Constantine Tsounis, Yuwei Yang, Jian Pan, Rose Amal","doi":"10.1021/acscatal.4c01510","DOIUrl":"https://doi.org/10.1021/acscatal.4c01510","url":null,"abstract":"Electrochemical nitrate reduction reaction (NO<sub>3</sub><sup>–</sup>RR) offers an alternative pathway toward ambient ammonia production and nitrogen balance restoration, requiring efficient catalysts. In this study, a silver-decorated cobalt oxide (Ag–Co<sub>3</sub>O<sub>4</sub>) catalyst was shown to enhance ammonia production during NO<sub>3</sub><sup>–</sup>RR in an alkaline electrolyte. Specifically, the Ag–Co<sub>3</sub>O<sub>4</sub> catalyst delivers an ammonia (NH<sub>3</sub>) yield rate of 52 μmol h<sup>–1</sup> cm<sup>–2</sup> with a Faradaic efficiency of 88% at −0.32 V versus RHE. The activity is 6 times higher than that of the conventional Co<sub>3</sub>O<sub>4</sub> catalyst (8.8 μmol h<sup>–1</sup> cm<sup>–2</sup>). The catalytic activity and selectivity of Ag–Co<sub>3</sub>O<sub>4</sub> originate from the interaction between atomically dispersed Ag and Co<sub>3</sub>O<sub>4</sub>, resulting in the formation of active octahedral Co<sup>2+</sup> species (Co<sup>2+</sup><sub>Oh</sub>) with an unpaired <i>e</i><sub><i>g</i></sub> electron, which facilitates the activation and adsorption of NO<sub>3</sub><sup>–</sup> ion and promotes the *NO<sub>2</sub> adsorption, along with its transformation to *NO intermediate. This leads to efficient NH<sub>4</sub><sup>+</sup> production, as evidenced by combined experimental and theoretical studies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Promoted Surface-Interface Catalysis over Mn–Cr Incorporated Cu-Based Catalysts for Efficient Hydrogen Production from Methanol Decomposition 促进锰铬结合铜基催化剂的表面-界面催化,从甲醇分解中高效制氢
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-12 DOI: 10.1021/acscatal.4c02918
Zhineng Tan, Guoli Fan, Lirong Zheng, Feng Li
{"title":"Promoted Surface-Interface Catalysis over Mn–Cr Incorporated Cu-Based Catalysts for Efficient Hydrogen Production from Methanol Decomposition","authors":"Zhineng Tan, Guoli Fan, Lirong Zheng, Feng Li","doi":"10.1021/acscatal.4c02918","DOIUrl":"https://doi.org/10.1021/acscatal.4c02918","url":null,"abstract":"To solve the safety problems and economic inefficiency of transporting and storing gaseous hydrogen, developing efficient catalytic decomposition of liquid organic hydrogen carriers for in situ hydrogen production is attracting more and more attention. Here, a series of Cr-doped, Mn-promoted Cu-based catalysts for methanol decomposition were fabricated from quaternary Cu–Mn–Cr–Al layered double hydroxides. It was demonstrated that Mn incorporation promoted the reduction and dispersion of copper species and regulated the electronic properties of surface metallic Cu sites, and an appropriate amount of Cr doping facilitated the generation of smaller Cu particles and reduced the surface acidity over catalysts, thereby favoring the construction of generous interfacial Cu<sup>+</sup> sites in the form of Cu<sup>+</sup>–O<sub>v</sub>–Mn and Cu<sup>+</sup>–O–M structures (O<sub>v</sub>: oxygen vacancy; M = Mn or Cr). The Cu-based catalyst bearing a Cr:Mn molar ratio of 0.4 achieved a high hydrogen selectivity of 84.3% at complete methanol conversion, along with long-term stability during 80 h of reaction. Through various exhaustive characterization studies, in situ diffuse reflectance infrared Fourier transform spectra of methanol adsorption and desorption, and density functional theory calculations, it was revealed that abundant interfacial Cu<sup>+</sup>–O<sub>v</sub>–Mn and Cu<sup>+</sup>–O–M structures and favorable Cu<sup>+</sup>–Cu<sup>0</sup> synergistic effects in Cu-based catalysts efficiently promoted a series of dehydrogenation processes of methanol and reaction intermediates, thus boosting hydrogen production. This study provides effective methods for the construction of Cu-based catalysts by engineering surficial and interfacial sites conducive to the efficient hydrogen production through methanol decomposition.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Operando Soft X-ray Absorption of LaMn1–xCoxO3 Perovskites for CO Oxidation 用于 CO 氧化的 LaMn1-xCoxO3 Perovskites 的操作性软 X 射线吸收
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-12 DOI: 10.1021/acscatal.4c03259
Qijun Che, Mahnaz Ghiasi, Luca Braglia, Matt L. J. Peerlings, Silvia Mauri, Piero Torelli, Petra de Jongh, Frank M. F. de Groot
{"title":"Operando Soft X-ray Absorption of LaMn1–xCoxO3 Perovskites for CO Oxidation","authors":"Qijun Che, Mahnaz Ghiasi, Luca Braglia, Matt L. J. Peerlings, Silvia Mauri, Piero Torelli, Petra de Jongh, Frank M. F. de Groot","doi":"10.1021/acscatal.4c03259","DOIUrl":"https://doi.org/10.1021/acscatal.4c03259","url":null,"abstract":"We employed operando soft X-ray absorption spectroscopy (XAS) to monitor the changes in the valence states and spin properties of LaMn<sub>1–<i>x</i></sub>Co<sub><i>x</i></sub>O<sub>3</sub> catalysts subjected to a mixture of CO and O<sub>2</sub> at ambient pressure. Guided by simulations based on charge transfer multiplet theory, we quantitatively analyze the Mn and Co 2p XAS as well as the oxygen K-edge XAS spectra during the reaction process. The Mn sites are particularly sensitive to the catalytic reaction, displaying dynamics in their oxidation state. When Co doping is introduced (<i>x</i> ≤ 0.5), Mn oxidizes from Mn<sup>2+</sup> to Mn<sup>3+</sup> and Mn<sup>4+</sup>, while Co largely maintains a valence state of Co<sup>2+</sup>. In the case of LaCoO<sub>3</sub>, we identify high-spin and low-spin Co<sup>3+</sup> species combined with Co<sup>2+</sup>. Our investigation underscores the importance to consider the spin and valence states of catalyst materials under operando conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597435","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Decatungstate/Cobalt Dual Catalyzed Dehydrogenation of Ketones Enabled by Polarity-Matched Site-Selective Activation 通过极性匹配的位点选择性活化实现癸钨酸盐/钴双催化酮的脱氢反应
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c02956
Bin Sun, Jiayin Wang, Shuangshuang Zhou, Jiaxing Xu, Xiaohui Zhuang, Zehui Meng, Yifan Xu, Zhiguo Zhang, Can Jin
{"title":"Decatungstate/Cobalt Dual Catalyzed Dehydrogenation of Ketones Enabled by Polarity-Matched Site-Selective Activation","authors":"Bin Sun, Jiayin Wang, Shuangshuang Zhou, Jiaxing Xu, Xiaohui Zhuang, Zehui Meng, Yifan Xu, Zhiguo Zhang, Can Jin","doi":"10.1021/acscatal.4c02956","DOIUrl":"https://doi.org/10.1021/acscatal.4c02956","url":null,"abstract":"The direct dehydrogenation of ketones has been widely utilized in both academic and industrial settings as the most efficient means of constructing unsaturated ketones and phenols. In contrast to the induction of dehydrogenation at the α-site of carbonyl by enol activation, direct and efficient activation of the carbonyl β-C(sp<sup>3</sup>)-H bond to form unsaturated ketones remains unexplored. Herein, we report a polarity-matching-based activation strategy for the carbonyl β-C(sp<sup>3</sup>)-H bond, enabling the photoinduced intramolecular dehydrogenation of ketones without prefunctionalization via the merger of photoredox and cobalt catalysis. This photoinduced mode employs a benign and mild approach to construct unsaturated ketone and phenol skeletons via acceptorless catalytic dehydrogenation, showcasing potential applications in the field of drug synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Elucidation of the Stereochemical Mechanism of Cystathionine γ-Lyase Reveals How Substrate Specificity Constrains Catalysis 阐明胱硫醚γ-赖氨酸酶的立体化学机制揭示底物特异性如何制约催化作用
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c02281
Anna Zmich, Lydia J. Perkins, Craig Bingman, Andrew R. Buller
{"title":"Elucidation of the Stereochemical Mechanism of Cystathionine γ-Lyase Reveals How Substrate Specificity Constrains Catalysis","authors":"Anna Zmich, Lydia J. Perkins, Craig Bingman, Andrew R. Buller","doi":"10.1021/acscatal.4c02281","DOIUrl":"https://doi.org/10.1021/acscatal.4c02281","url":null,"abstract":"Pyridoxal phosphate (PLP)-dependent enzymes play essential roles in metabolism and have found applications for organic synthesis and as enzyme therapeutics. The vinylglycine ketimine (VGK) subfamily hosts a growing set of enzymes that play diverse roles in primary and secondary metabolism. However, the molecular determinants of substrate specificity and the complex acid–base chemistry that enables VGK catalysis remain enigmatic. We use a recently discovered amino acid γ-lyase as a model system to probe catalysis in this enzyme family. We discovered that two stereochemically distinct proton transfer pathways occur. Combined kinetic and spectroscopic analysis revealed that progression through the catalytic cycle is correlated with the presence of an H-bond donor after Cγ of an amino acid substrate, suggesting that substrate binding is kinetically coupled to a conformational change. High-resolution X-ray crystallography shows that cystathionine-γ-lyases generate an <i>s-trans</i> intermediate and that this geometry is likely conserved throughout the VGK family. An H-bond acceptor in the active site templates substrate binding but does so by preorganizing substrates <i>away</i> from catalytically productive orientations. Mutagenesis eliminates this preorganization, such that there is a relaxation of the substrate specificity but an increase in <i>k</i><sub>cat</sub> for diverse substrates. We exploit this information to perform a preparative-scale α,β,β-trideuteration of polar amino acids. Together, these data untangle a complex mode of substrate specificity and provide a foundation for the future study and applications of VGK enzymes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Anionic Olefin Metathesis Catalysts Enable Modification of Unprotected Biomolecules in Water 阴离子烯烃官能团催化剂可在水中修饰未受保护的生物分子
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c02811
Christian O. Blanco, Richard Ramos Castellanos, Deryn E. Fogg
{"title":"Anionic Olefin Metathesis Catalysts Enable Modification of Unprotected Biomolecules in Water","authors":"Christian O. Blanco, Richard Ramos Castellanos, Deryn E. Fogg","doi":"10.1021/acscatal.4c02811","DOIUrl":"https://doi.org/10.1021/acscatal.4c02811","url":null,"abstract":"Stability problems have limited the uptake of cationic olefin metathesis catalysts in chemical biology. Described herein are anionic catalysts that improve water-solubility, robustness, and compatibility with biomolecules such as DNA. A sulfonate tag is installed on the cyclic (alkyl)(amino) carbene (CAAC) ligand platform, chosen for resistance to degradation by nucleophiles, base, water, and β-elimination. Hoveyda–Grubbs catalysts bearing the sulfonated CAAC ligands deliver record productivity in metathesis of unprotected carbohydrates and nucleosides at neutral pH. Decomposed catalyst has negligible impact on metathesis selectivity, whereas N-heterocyclic carbene (NHC) catalysts degrade rapidly in water and cause extensive C=C migration.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588832","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Activation Heat Capacities in Pyridoxal Phosphate Enzymes 磷酸吡哆醛酶的活化热容量
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c01959
Jake P. Erbez, Griffin H. Rangel, Mia Davila, Jackson A. Englade, Alexander D. Erbez, Jasmine Rattanpal, Haocheng Li, Yuezhou Chen, Michael D. Toney
{"title":"Activation Heat Capacities in Pyridoxal Phosphate Enzymes","authors":"Jake P. Erbez, Griffin H. Rangel, Mia Davila, Jackson A. Englade, Alexander D. Erbez, Jasmine Rattanpal, Haocheng Li, Yuezhou Chen, Michael D. Toney","doi":"10.1021/acscatal.4c01959","DOIUrl":"https://doi.org/10.1021/acscatal.4c01959","url":null,"abstract":"Much attention has been given to the temperature dependence of enzyme catalyzed reaction rates in the last ∼100 years. Over the last couple of decades, it has become apparent that activity decreases before enzymes lose their structural integrity. Two viable models have been proposed to account for this behavior. In one, an inactive conformation(s) becomes more populated at higher temperatures. In the other, a difference in heat capacity between ground and transition state conformational ensembles is invoked. Here, the temperature dependence of the activity of 16 different combinations of pyridoxal phosphate enzymes and substrates has been measured. All show non-Arrhenius activity vs temperature profiles. These are generally best accommodated by the second model where the Δ<i>G</i><sup>‡</sup> term in the Eyring equation is expanded in terms of Δ<i>H</i><sup>‡</sup>, Δ<i>S</i><sup>‡</sup>, and Δ<i>C</i><sub>p</sub><sup>‡</sup> (macromolecular rate theory (MMRT) equation). The values of Δ<i>C</i><sub>p</sub><sup>‡</sup> extracted by curve fitting are negative and in the range of −1 to −2 kJ/(mol K). Several data sets fit better to a modified MMRT equation that additionally includes the temperature dependence of Δ<i>C</i><sub>p</sub><sup>‡</sup> (dΔ<i>C</i><sub>p</sub><sup>‡</sup>/d<i>T</i>). The values of dΔ<i>C</i><sub>p</sub><sup>‡</sup>/d<i>T</i> from curve fitting are also negative. The additional dΔ<i>C</i><sub>p</sub><sup>‡</sup>/d<i>T</i> term has major effects on temperature profiles at the low and high ends of the biological temperature range. Molecular dynamics simulations using the AMBER-FB15 force field were performed on a set of six model proteins and two of the enzymes studied experimentally. Convex energy vs temperature relationships are observed, which require a positive d<i>C</i><sub>p</sub>/d<i>T</i> term to fit the data well. The simulations for ground and transition state structures for aspartate aminotransferase and <span>d</span>-serine deaminase allow calculation of Δ<i>C</i><sub>p</sub><sup>‡</sup> and dΔ<i>C</i><sub>p</sub><sup>‡</sup>/d<i>T</i> for comparison to experiments. Negative values for Δ<i>C</i><sub>p</sub><sup>‡</sup> and dΔ<i>C</i><sub>p</sub><sup>‡</sup>/d<i>T</i> are obtained for both enzymes. The simulations generally reproduce well the experimental values of Δ<i>C</i><sub>p</sub><sup>‡</sup> but the dΔ<i>C</i><sub>p</sub><sup>‡</sup>/d<i>T</i> values are overestimated. The results support a model in which a large, looser ensemble of ground state-compatible conformations is in equilibrium with a very small, tighter transition state-optimized ensemble that allows bond making and breaking to occur with a low energetic barrier.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597436","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Pd-Methylnaphthyl-tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine Pd-Methylnaphthyl-tBuBrettPhos 复合物作为氨和肼单芳基化的高效选择性催化剂
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c02624
Bingxiang Xue, Florian Papp, Muyang Yang, Jie Shen, Angelino Doppiu, Lukas J. Gooßen
{"title":"Pd-Methylnaphthyl-tBuBrettPhos Complexes as Efficient and Selective Catalysts for the Monoarylation of Ammonia and Hydrazine","authors":"Bingxiang Xue, Florian Papp, Muyang Yang, Jie Shen, Angelino Doppiu, Lukas J. Gooßen","doi":"10.1021/acscatal.4c02624","DOIUrl":"https://doi.org/10.1021/acscatal.4c02624","url":null,"abstract":"Only a few sterically crowded ligands promote palladium-catalyzed, selective monoarylations of ammonia and hydrazine. We herein demonstrate that the formation of palladium precatalysts bearing such ligands is the limiting factor in these reactions, and we present bench-stable, Pd-methylnaphthyl (MeNAP)-<sup>t</sup>BuBrettPhos complexes as effective catalysts. X-ray and spectroscopic analyses have revealed that the biaryl system of the ligand reversibly inserts into the Pd-(MeNAP)C bond during complex formation. The performance of MeNAP complexes is shown to be a consequence of their clean formation and rapid activation. Their preparative utility is demonstrated by the synthesis of 32 anilines and arylhydrazines.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Regulating the Oxygen Vacancy of 3R-Phase Iridium Oxide by Loading Platinum Nanoparticles for Efficient Hydrogen Evolution 通过添加铂纳米粒子调节 3R 相氧化铱的氧空位以实现高效氢气转化
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c02062
Ruiqi Guo, Jiajie Wang, Jiayi Li, Huaqing Li, Huihua Wang, Yi Cao, Jinxin Chen, Tao Cheng, Hao Yang, Minqi Sheng
{"title":"Regulating the Oxygen Vacancy of 3R-Phase Iridium Oxide by Loading Platinum Nanoparticles for Efficient Hydrogen Evolution","authors":"Ruiqi Guo, Jiajie Wang, Jiayi Li, Huaqing Li, Huihua Wang, Yi Cao, Jinxin Chen, Tao Cheng, Hao Yang, Minqi Sheng","doi":"10.1021/acscatal.4c02062","DOIUrl":"https://doi.org/10.1021/acscatal.4c02062","url":null,"abstract":"Balancing the activity and stability of electrocatalytic composites in the acidic hydrogen evolution reaction (HER) is still a great challenge. Although 3R-phase iridium oxide (3R-IrO<sub>2</sub>) is recognized as a potential competitor for the acidic oxygen evolution reaction (OER), its other catalytic activities have not been explored. Herein, 3R-IrO<sub>2</sub> modified by Pt nanoparticles (Pt@3R-IrO<sub>2</sub>) exhibits certain catalytic activity toward the acidic HER. The Pt@3R-IrO<sub>2</sub> with 15 wt % Pt loading (15 wt % Pt@3R-IrO<sub>2</sub>) displays high HER activity with a low overpotential (η@–10 mA cm<sup>–2</sup>) of 19.0 mV, a high mass activity of 0.77 A mg<sub>Ir+Pt</sub><sup>–1</sup> and considerable economic effect of 5.54 A $<sup>–1</sup> at −0.03 V vs RHE. Moreover, the 15 wt % Pt@3R-IrO<sub>2</sub> electrocatalyst can maintain the HER process in 0.5 M H<sub>2</sub>SO<sub>4</sub> for more than 300 h under continuous current changes. Theoretical calculations prove that loading Pt nanoparticles can properly regulate the HER catalytic activity of 3R-IrO<sub>2</sub>, mainly for the following two reasons: (i) loading Pt atoms/clusters on 3R-IrO<sub>2</sub> can reduce the formation energy of oxygen vacancy, thus facilitating the exposure of unsaturated Ir atoms as the active sites, and (ii) the Ir 5d band center for Pt@3R-IrO<sub>2</sub> is moderately modified, indicating that it is beneficial to weaken the Gibbs free energy of hydrogen adsorption (Δ<i>G</i><sub>*H</sub>).","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Dynamic Bromine Vacancy-Mediated Photocatalytic Three-Step Three-Electron Oxygen Reduction to Hydroxyl Radicals 动态溴空位介导的光催化三步三电子氧还原羟基自由基
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2024-07-11 DOI: 10.1021/acscatal.4c02674
Na Wen, Yingping Huang, Yuantao Yang, Hankun Wang, Decheng Wang, Haohao Chen, Qintian Peng, Xing Ying Kong, Liqun Ye
{"title":"Dynamic Bromine Vacancy-Mediated Photocatalytic Three-Step Three-Electron Oxygen Reduction to Hydroxyl Radicals","authors":"Na Wen, Yingping Huang, Yuantao Yang, Hankun Wang, Decheng Wang, Haohao Chen, Qintian Peng, Xing Ying Kong, Liqun Ye","doi":"10.1021/acscatal.4c02674","DOIUrl":"https://doi.org/10.1021/acscatal.4c02674","url":null,"abstract":"Hydroxyl radicals (•OH), recognized for their strong oxidizing ability, have garnered extensive attention in the field of photocatalysis. However, as a two-dimensional layered material widely employed in the field of environmental photocatalysis, BiOBr is incapable of catalyzing the generation of •OH, severely impeding its efficient degradation of organic pollutants. In this paper, we propose an efficient approach to generate •OH by expanding the spacing between crystal faces. Through the expansion of the {001} crystal face spacing of BiOBr, we synthesized ultrathin BiOBr-3 nanosheets with reduced bond energy of the Bi–Br bond, which favored the precipitation of Br<sup>–</sup> and the formation of bromine vacancies (Br<sub>V</sub>) under photocatalytic conditions, thereby promoting the efficient activation of molecular oxygen to generate •OH. The mechanism of photocatalytic reduction of molecular oxygen to hydroxyl radicals by three steps and three electrons was elucidated by in situ infrared spectroscopy and free radical probe experiments. Density functional theory calculations indicated that BiOBr-3 containing bromine vacancies significantly reduced the free energy barrier of *OOH, facilitating the formation of H<sub>2</sub>O<sub>2</sub> and the reduction to •OH. In comparison to BiOBr without Br<sub>V</sub>, BiOBr-3 containing Br<sub>V</sub> demonstrated higher photoactivity toward degradation of triazine organic pollutants. The toxicity of the atrazine degradation solution was significantly reduced through the use of the toxicity estimation software tool and quantitative structure–activity relationship-based methods, as well as HepG2 cell viability detection.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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