ACS Catalysis 最新文献_第3页

Modulating Chloride Adsorption for Efficient Chloride-Mediated Methane Conversion over Tungsten Oxide Photoanode

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-30 DOI: 10.1021/acscatal.4c07046

Jun Ma, Keke Mao, Jiayi Li, Guangyao Zhai, Di Wu, Dong Liu, Ran Long, Yujie Xiong

{"title":"Modulating Chloride Adsorption for Efficient Chloride-Mediated Methane Conversion over Tungsten Oxide Photoanode","authors":"Jun Ma, Keke Mao, Jiayi Li, Guangyao Zhai, Di Wu, Dong Liu, Ran Long, Yujie Xiong","doi":"10.1021/acscatal.4c07046","DOIUrl":"https://doi.org/10.1021/acscatal.4c07046","url":null,"abstract":"Utilizing alkali chlorides as the chloride source in chloride-mediated methane activation represents an efficient approach for CH4 valorization. Nevertheless, great challenges remain due to the restricted catalytic activity and durability. Here, we present a photoelectrochemical approach for chloride-mediated methane conversion to C1 products using WO3 with surface oxygen vacancies (OV). Theoretical calculations indicate that oxygen vacancies play a crucial role in enhancing chloride adsorption to facilitate methane activation. The engineered WO3–OV photoanode exhibits enhanced catalytic performance in comparison to the pristine counterparts, attaining a Faradaic efficiency of 94.5% for C1 products (methyl chloride, methanol, formic acid, and formaldehyde) at 0.9 V vs RHE. This performance corresponds to a total production rate of 139.2 mmol g–1 h–1 for the C1 products. Furthermore, the system is capable of achieving a high CH4 conversion efficiency of 11.8%. This work emphasizes the pivotal role of photoanode design and surface engineering in facilitating methane conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"31 1","pages":"6058-6066"},"PeriodicalIF":12.9,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736355","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

Direct Comparison of the Activity and Selectivity of Rh1Cu and Ni1Cu Single-Atom Alloy Sites for Ethanol Decomposition

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-29 DOI: 10.1021/acscatal.4c07556

Yicheng Wang, Hio Tong Ngan, Ho-Yi Lam, George Yan, Ryan T. Hannagan, Volkan Çınar, Nathaniel M. Eagan, Prashant Deshlahra, Philippe Sautet, E. Charles H. Sykes

{"title":"Direct Comparison of the Activity and Selectivity of Rh1Cu and Ni1Cu Single-Atom Alloy Sites for Ethanol Decomposition","authors":"Yicheng Wang, Hio Tong Ngan, Ho-Yi Lam, George Yan, Ryan T. Hannagan, Volkan Çınar, Nathaniel M. Eagan, Prashant Deshlahra, Philippe Sautet, E. Charles H. Sykes","doi":"10.1021/acscatal.4c07556","DOIUrl":"https://doi.org/10.1021/acscatal.4c07556","url":null,"abstract":"Ethanol is an important source of clean hydrogen, acetaldehyde, acetic acid, acetate esters, and light hydrocarbons. Controlling the divergent reaction pathways to these products requires understanding how different active sites influence the elementary steps involved. Herein, we present a combined surface science, theory, and nanoparticle catalysis study demonstrating how two single-atom dopants (Rh and Ni) in a Cu host can distinctively alter the selectivity of alcohol conversion. Specifically, our model studies reveal that ethanol reacts on Ni1Cu single-atom alloys to selectively produce acetaldehyde, whereas methane and CO are also formed on Rh1Cu single-atom alloys. Interestingly, these different reactivities are in contrast to the behavior of the pure metals as Ni(111) and Rh(111) surfaces favor methane/CO and surface carbon/CO, respectively. DFT calculations of reaction pathways and simulated product desorption based on microkinetic analyses explain these reactivity differences, demonstrating that C–C cleavage leading to methane formation has a lower barrier on Rh single-atom sites. To test the catalytic relevance of these fundamental results we synthesized and characterized supported Ni1Cu and Rh1Cu single-atom alloy nanoparticles with dopant:Cu ratios of 1:200. Flow reactor results revealed that both Ni and Rh increased ethanol conversion over Cu and that Ni1Cu catalysts were >99.9% selective to acetaldehyde, while Rh1Cu also produced 0.6%–2.6% of equimolar methane and CO between 433 and 493 K, demonstrating that C–C bond cleavage is enabled by isolated Rh sites. These catalytic results bridge the pressure and materials gaps, and together, this study provides insights into how different isolated dopant sites promote different catalytic pathways.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":"6046-6057"},"PeriodicalIF":12.9,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736354","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

Modulating Local Proton Coverage and *OOH Generation via Coupled Multiple Sites for Enhanced Photocatalytic H2O2 Production

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-29 DOI: 10.1021/acscatal.5c01205

Wengao Zeng, Yuchen Dong, Xiaoyuan Ye, Yi Zhao, Ziying Zhang, Tuo Zhang, Lei Zhang, Jie Chen, Xiangjiu Guan

{"title":"Modulating Local Proton Coverage and *OOH Generation via Coupled Multiple Sites for Enhanced Photocatalytic H2O2 Production","authors":"Wengao Zeng, Yuchen Dong, Xiaoyuan Ye, Yi Zhao, Ziying Zhang, Tuo Zhang, Lei Zhang, Jie Chen, Xiangjiu Guan","doi":"10.1021/acscatal.5c01205","DOIUrl":"https://doi.org/10.1021/acscatal.5c01205","url":null,"abstract":"Rationally modulating the adsorption of reaction intermediates on the surface sites of carbon nitride-based catalysts could facilitate the photocatalytic reduction of O2 to H2O2. Herein, theoretical calculations reveal that multiple sites of heteroatoms and defects can synergistically increase local proton coverage and lower the kinetic barrier for O2 protonation, thereby promoting the production of *OOH and the subsequent generation of H2O2. As a proof of concept, carbon nitride (BPMC-Vs) with multiheteroatoms (B and P) and multidefects (N defects, ─C≡N) was successfully synthesized, achieving optimized solar-to-chemical conversion efficiency and selectivity of 0.33% and 95.2%, respectively. In situ spectroscopic characterization combined with theoretical calculations confirms that P atoms and ─C≡N groups increase proton coverage, while B atoms and N defects effectively promote the protonation of O2 to *OOH, thereby significantly enhancing the generation of H2O2. This work provides insightful guidance for carbon nitride catalysis at the atomic scale for boosting photocatalytic H2O2 production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"95 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734397","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

Conditions-Controlled Divergent Annulation of Bicyclo[1.1.0]butanes and Dioxopyrrolidines through Lewis Acid Catalysis

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-28 DOI: 10.1021/acscatal.4c07205

Jun-Long Li, Chuan Xie, Rong Zeng, Wen-Chao Yuan, Yuan-Yuan Lei, Ting Qi, Hai-Jun Leng, Qing-Zhu Li

引用次数: 0

C4-Symmetric Inherently Chiral Macrocycles from Organocatalytic Enantioselective Desymmetrization of Resorcin[4]arenes

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-28 DOI: 10.1021/acscatal.5c00340

Hui Han, Xin-Ge Wang, Shuo Tong, Jieping Zhu, Mei-Xiang Wang

引用次数: 0

Metal- and Site-Specific Roles of High-Entropy Spinel Oxides in Catalytic Oxidative Polymerization of Water Contaminants

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.5c00854

Yalan Mo, Zhihao Tian, Kunsheng Hu, Wei Ren, Xiao Lu, Xiaoguang Duan, Shaobin Wang

{"title":"Metal- and Site-Specific Roles of High-Entropy Spinel Oxides in Catalytic Oxidative Polymerization of Water Contaminants","authors":"Yalan Mo, Zhihao Tian, Kunsheng Hu, Wei Ren, Xiao Lu, Xiaoguang Duan, Shaobin Wang","doi":"10.1021/acscatal.5c00854","DOIUrl":"https://doi.org/10.1021/acscatal.5c00854","url":null,"abstract":"High-entropy spinel oxides (HESOs) have emerged as promising catalysts due to their multimetal interactions, compositional flexibility, and superior structural stability; however, the roles of each metal in catalytic reactions remain elusive. In addition, catalytic organic recycling via polymerization has attracted increasing attention as a sustainable strategy for wastewater treatment. Herein, we synthesized HESOs incorporating five transition metals (Fe, Co, Ni, Cr, and Mn) using a low-temperature microwave-assisted method to achieve highly dispersed metal species in nanoparticles for catalytic peroxymonosulfate (PMS) activation for organic transformation and elucidate the different metal site catalysis. Comprehensive characterizations confirmed the single-phase spinel structure, high configurational entropy, and site-selective cation distribution among the tetrahedral and octahedral sites within the HESOs. The HESOs demonstrated superior activity in PMS activation for the polymerization of bisphenol A (BPA), outperforming single metal-based oxides. Mechanistic studies revealed that BPA degradation followed a nonradical electron transfer pathway mediated by surface catalyst-PMS* complexes. The enhanced catalytic activity was attributed to the distinct roles of individual metal components at different sites: Co served as the predominant electron donor, Cr facilitated strong PMS adsorption, and Ni supported the redox cycling of Co2+/Co3+. These metal-specific contributions synergistically enhanced the PMS activation efficiency, enabling BPA removal via oxidative polymerization with minimal oxidant consumption. Overall, this work provides in-depth insights into the metal- and site-specific roles in multisite synergy of HESOs and demonstrates their innovative application in Fenton-like catalysis toward fast water decontamination in a more selective and low-chemical-consumption manner for carbon recycling.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"125 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713368","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

Retreat in Order to Advance: Dual-Electrode Refinery of 5-Hydroxymethylfurfural toward 2,5-Furandicarboxylic Acid with High Carbon Efficiency

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.5c01243

Zhuxin Gui, Yingshuai Jia, Wenbiao Zhang, Ying Liang, Yizhong Chen, Tianlan Yan, Qingsheng Gao, Yahong Zhang, Yi Tang

{"title":"Retreat in Order to Advance: Dual-Electrode Refinery of 5-Hydroxymethylfurfural toward 2,5-Furandicarboxylic Acid with High Carbon Efficiency","authors":"Zhuxin Gui, Yingshuai Jia, Wenbiao Zhang, Ying Liang, Yizhong Chen, Tianlan Yan, Qingsheng Gao, Yahong Zhang, Yi Tang","doi":"10.1021/acscatal.5c01243","DOIUrl":"https://doi.org/10.1021/acscatal.5c01243","url":null,"abstract":"Electro-refinery of 5-hydroxymethylfurfural (HMF) is an ecofriendly route to upgrade biomass feedstock under ambient conditions, producing high-value-added 2,5-furandicarboxylic acid (FDCA) and 2,5-bis(hydroxymethyl)furan (BHMF). However, FDCA electrosynthesis suffers from serious carbon loss due to HMF self-polymerization in the conventional alkaline electrolyte, emphasizing the protection of HMF via hydrogenation to robust BHMF for subsequent oxidation. Herein, dual-electrode HMF tandem refinery (DEHTR) integrated via cathodic protection and anodic oxidation, as the strategy of “retreat in order to advance” for FDCA electrosynthesis, was proposed. We developed a series of Cu-based cathodic/anodic catalysts by the alternating electrochemical treatments of copper foam, precisely regulating the active site amount/structure to accomplish the efficient HMF electro-hydrogenation (90.3% HMF conversion, 94.3% BHMF selectivity, and 86.3% FE) as well as BHMF electro-oxidation (99.3% FDCA yield and 95.5% FE). On this basis, DEHTR was finely constructed over an optimized Cu-based cathode/anode, which was expanded to a membrane-free flow electrolysis system, acquiring a higher FDCA yield and a carbon balance of 95.1% (vs 65.2% in direct HMF electro-oxidation) even at a large HMF concentration (100 mM). Moreover, gram-scale FDCA powder with 99.1% purity was simply separated from the DEHTR flow system. This work sheds light on the development of biomass electro-refinery with high carbon efficiency by collaboratively integrating dual-electrode procedures on cost-efficient electrocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723936","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

NHC-Cracker: A Platform for the In Silico Engineering of N-Heterocyclic Carbenes for Diverse Chemical Applications

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.4c06474

Gentoku Takasao, Bholanath Maity, Sayan Dutta, Rajesh Kancherla, Magnus Rueping, Luigi Cavallo

{"title":"NHC-Cracker: A Platform for the In Silico Engineering of N-Heterocyclic Carbenes for Diverse Chemical Applications","authors":"Gentoku Takasao, Bholanath Maity, Sayan Dutta, Rajesh Kancherla, Magnus Rueping, Luigi Cavallo","doi":"10.1021/acscatal.4c06474","DOIUrl":"https://doi.org/10.1021/acscatal.4c06474","url":null,"abstract":"We present an in silico workflow to streamline the identification of promising N-heterocyclic carbenes (NHCs) as ligands in metal catalysis or as catalysts in organocatalysis. Central to this workflow is the NHC-cracker database, which contains over 200 descriptors for 1781 nonredundant NHCs, each documented as an NHC-metal complex in the Cambridge Structural Database. To demonstrate its utility, we applied it to two catalytic problems using literature data. First, we analyzed 21 Ru–NHC complexes active in the ethenolysis of cyclic olefins. An MLR (multivariate linear regression) model trained on 11 Ru complexes based on NHCs in NHC-cracker successfully rationalized the behavior of the remaining 10 complexes. Second, we examined an Ir–Ni dual-catalyzed Csp2–Csp3 cross-coupling reaction involving five experimentally tested NHC skeletons. Using a multiscale workflow, we created DFT-based data sets to train two MLR models: one for productive substrate activation and another for detrimental NHC dimerization. Consistent with experiments, the models identified oxazoles as reactive, while benzimidazoles, triazoles, thiazoles, and untested cyclic (alkyl)(amino)carbenes were predicted as nonreactive. Experimental validation confirmed the latter’s lack of productive substrate activation, supporting the proposed mechanistic scenario.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713366","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

Rational Engineering of Self-Sufficient P450s to Boost Catalytic Efficiency of Carbene-Mediated C–S Bond Formation

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.5c01569

Binhao Wang, Tai-Ping Zhou, Yu Shen, Jie Hu, Jieyu Zhou, Jin Tang, Ruizhi Han, Guochao Xu, Ulrich Schwaneberg, Binju Wang, Ye Ni

{"title":"Rational Engineering of Self-Sufficient P450s to Boost Catalytic Efficiency of Carbene-Mediated C–S Bond Formation","authors":"Binhao Wang, Tai-Ping Zhou, Yu Shen, Jie Hu, Jieyu Zhou, Jin Tang, Ruizhi Han, Guochao Xu, Ulrich Schwaneberg, Binju Wang, Ye Ni","doi":"10.1021/acscatal.5c01569","DOIUrl":"https://doi.org/10.1021/acscatal.5c01569","url":null,"abstract":"Intermolecular C–S bond formation is a key step in the construction of sulfur-containing compounds in organic chemistry. As versatile biocatalysts, P450-catalyzed radical reactions are compatible with a diverse range of functional groups. Here, to boost the catalytic efficiency of carbene-mediated C–S bond formation, self-sufficient P450TT was rationally engineered using multiple AI models (SaProt, ProSST, EVmutation). Employing purified enzymes, a triple variant P450TT-M3 (V118A/C385H/F424P) demonstrated a significantly higher TOF of 6.1 min–1 than that of P450TT-M1(C385H) (1.5) in 1 h. Furthermore, with remarkable adaptability to a diverse range of aryl mercaptans, it exhibits high versatility in catalyzing the formation of intermolecular C–S bonds. Computational studies have shown that C–S bond formation involved H atom transfer from the thiol group of thiophenol to Fe-carbene, which differs from P450-catalyzed N–H insertion reactions. In addition, QM/MM simulations suggested that the variant enables a further approach of ethyl diazoacetate to the iron center, thereby enhancing the catalytic efficiency.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"36 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723958","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

Unlocking Methanol Synthesis from CO2 and H2 on ZnO/ZrO2 Catalysts: Surface Hydroxyl-Mediated Activation

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.5c01585

Haohao Chang, Feifan Gao, Sicong Ma, Yifeng Zhu, Zhipan Liu, Junhui Liu, Heyong He, Keke Zhang, Yongmei Liu, Yong Cao

{"title":"Unlocking Methanol Synthesis from CO2 and H2 on ZnO/ZrO2 Catalysts: Surface Hydroxyl-Mediated Activation","authors":"Haohao Chang, Feifan Gao, Sicong Ma, Yifeng Zhu, Zhipan Liu, Junhui Liu, Heyong He, Keke Zhang, Yongmei Liu, Yong Cao","doi":"10.1021/acscatal.5c01585","DOIUrl":"https://doi.org/10.1021/acscatal.5c01585","url":null,"abstract":"ZnO/ZrO2 catalysts show promise for CO2-to-methanol conversion, but the challenge of effective CO2 and H2 adsorption and activation hinders efficiency. Herein, we address this issue by systematically adjusting the calcination temperature of m-ZrO2 and optimizing interfacial interactions, which results in the suppression of terminal and hydrogen-bonded hydroxyl groups that hinder catalytic activity and the enrichment of interfacial and bridging hydroxyl groups that facilitate methanol synthesis. The combination of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), solid-state nuclear magnetic resonance (ssNMR), and density functional theory (DFT) calculations has elucidated that interfacial hydroxyl groups (Zn–OH–Zr) activate CO2, forming the metastable bicarbonate species, which is essential for the formate pathway of methanol synthesis. Moreover, bridging hydroxyl groups (Zr–OH–Zr) facilitate proton transfer to intermediates, with adjacent ZnO clusters providing additional protons through H2 dissociation, thereby emphasizing the pivotal function of hydroxyl groups in the methanol production process. Based on these insights, we prepared the 20% ZnO–ZrO2–OG catalyst with highly dispersed ZnO and abundant bridging hydroxyl groups, achieving an 84% methanol selectivity and an ∼10% CO2 conversion at high space velocity. This revelation offers valuable insights and guides the way for the development of more efficient catalysts, essential for the advancement of effective carbon management.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"59 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723932","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