ACS Catalysis 最新文献_第5页

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

Promotional Effect of ZnO and ZrO2 in K-Doped Fe Catalysts for CO2 Hydrogenation to Light Olefins

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.4c07100

Min Wang, Lu-Cun Wang, Bin Liu, Yong Ding, Yingchao Yang, Dong Ding

{"title":"Promotional Effect of ZnO and ZrO2 in K-Doped Fe Catalysts for CO2 Hydrogenation to Light Olefins","authors":"Min Wang, Lu-Cun Wang, Bin Liu, Yong Ding, Yingchao Yang, Dong Ding","doi":"10.1021/acscatal.4c07100","DOIUrl":"https://doi.org/10.1021/acscatal.4c07100","url":null,"abstract":"Promoters play a critical role in tuning the activity and selectivity of Fe catalysts in CO2 hydrogenation to produce light olefins, which are key building blocks in the petrochemical industry. Herein, by a combined experimental and theoretical approach, we show that high and stable performance of Fe catalysts could be achieved by taking advantage of the promotional effect of both Zn and Zr. Structural characterization indicates that ZnO could improve the dispersion and reducibility of Fe oxides and facilitate the formation of active Fe carbide species, whereas ZrO2 could stabilize the structure and catalytic performance, especially the selectivity of hydrocarbon products. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments suggest that carbonate, bicarbonate, formate, and methoxy are essential intermediates in the CO2 hydrogenation to hydrocarbon products, including paraffins and olefins. The conversion kinetics of each intermediate species are dependent on the type of promoters as well as the phase structure of the active Fe species. DFT calculations revealed a strong correlation between the formation energy of surface oxygen vacancies and that of Fe carbide species in promoted Fe oxides, in accordance with experimental results. Moreover, the calculated energy profiles of CO2 hydrogenation over different catalysts indicate that Zn could promote the activation of CO2 and its transformation to the oxygenate intermediates, while Zr could facilitate the conversion of oxygenates to hydrocarbon precursors. The discrepancies in the evolution trend of various intermediate species on promoted Fe catalysts in the transient DRIFTS experiments can be rationalized by the differences in energy barriers of elementary or rate limiting steps.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"34 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723930","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

En Route to Direct Cross-Coupling between Carbonyl Derivatives and Allyl Alcohols via Hydrazones

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.4c07971

Ruohua Gui, Faraz Alaghemand, Rustam Z. Khaliullin, Chao-Jun Li

引用次数: 0

C4-Symmetric Bowl-Shaped Diruthenium Tetracarboxylate Catalysts for Enantioselective C–H Functionalization Using Donor/Acceptor Carbenes

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.5c01052

Joshua K. Sailer, John Bacsa, Huw M. L. Davies

引用次数: 0

Electrochemical Nitrate Reduction to Ammonia using γ-Fe2O3/BCN in a Neutral Medium