ACS Catalysis 最新文献_第2页

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

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-27 DOI: 10.1021/acscatal.5c00936

Soniya Mariya Varghese, Anju Vakakuzhiyil Gopinathan, Sudhin Rathnakumaran, Suraj Sasikumar, Sooraj Kunnikuruvan, Ranga Rao Gangavarapu

引用次数: 0

Modulating Pt States through Hydroxyl Control for Low-Temperature Aqueous Phase Reforming of Methanol

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-26 DOI: 10.1021/acscatal.5c00357

Yuyao Yang, Xuan Bie, Xiaoying Qi, Yongqing Xu, Qinghai Li, Yanguo Zhang, Hui Zhou

{"title":"Modulating Pt States through Hydroxyl Control for Low-Temperature Aqueous Phase Reforming of Methanol","authors":"Yuyao Yang, Xuan Bie, Xiaoying Qi, Yongqing Xu, Qinghai Li, Yanguo Zhang, Hui Zhou","doi":"10.1021/acscatal.5c00357","DOIUrl":"https://doi.org/10.1021/acscatal.5c00357","url":null,"abstract":"Aqueous phase reforming of methanol (APRM) offers a method for releasing H2 from the liquid phase, by which H2 can be stored in methanol safely. It is an efficient way to design high-performance catalysts by controlling the hydroxyl (OH) groups, but its mechanism for affecting the APRM is still unclear. Herein, we loaded Pt on three types of Al2O3 (nanopolyhedron, nanosheet, and nanorod Al2O3) with different OH contents and types. Among them, Pt/nanorod Al2O3 exhibited the highest H2 production rate of 20.4 μmol g–1 s–1 with 96.6% H2 selectivity at a low temperature of 190 °C. This was attributed to the roles of hydroxyl groups in modulating Pt states. On nanopolyhedron, nanosheet, and nanorod Al2O3, the bonding of Pt with O atoms became more favorable as the dehydroxylation happened. In particular, on nanorod Al2O3, the dehydroxylation process generated a high density of five-coordinated Al (AlV) sites, facilitating the dispersion and anchoring of Pt particles. Moreover, the special OH groups (hydrogen bond donor) on nanorod Al2O3 promoted Pt particle reduction via the movement of electrons. Ultimately, the results demonstrated the influence of OH groups on the dispersion and reduction of active metals, offering perspectives for designing catalysts for APRM through hydroxyl control.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"21 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703224","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

Dopant-Induced Electron Localization Drives Direct Current Kolbe Coupling of Biomass-Derived Carboxylic Acids

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-26 DOI: 10.1021/acscatal.5c00403

Wenhua Zhou, Bolong Li, Gaobo Lin, Teng Guo, Chao Chen, Jie Zhu, Haoan Fan, Xuezhi Zhao, Lei Guo, Weiyu Song, Jianghao Wang, Tianfu Wang, Jie Fu

{"title":"Dopant-Induced Electron Localization Drives Direct Current Kolbe Coupling of Biomass-Derived Carboxylic Acids","authors":"Wenhua Zhou, Bolong Li, Gaobo Lin, Teng Guo, Chao Chen, Jie Zhu, Haoan Fan, Xuezhi Zhao, Lei Guo, Weiyu Song, Jianghao Wang, Tianfu Wang, Jie Fu","doi":"10.1021/acscatal.5c00403","DOIUrl":"https://doi.org/10.1021/acscatal.5c00403","url":null,"abstract":"The Kolbe coupling of biomass-derived carboxylic acids presents a promising route for sustainable production of value-added chemicals. However, conventional direct current (DC) Kolbe electrolysis typically cleaves functional groups in carboxylic acids, significantly hindering its broader application. Herein, we demonstrate that dopant-induced electron localization in activated carbon (AC) facilitates decarboxylative coupling while preserving functional integrity. Experimental and theoretical results reveal that nitrogen doping in AC (N-AC) modulates the local electronic structure and enhances the adsorption capacity of carboxylic acids. Notably, N-AC exhibits a 10-fold increase in the conversion of 10-undecenoic acid compared to AC, with a selectivity of up to 60 ± 2% for the coupling product. More importantly, N-AC effectively catalyzes carboxylic acids with diverse functional groups. This study provides new insights into the structure–property relationship of N-doped carbon and advances the practical implementation of Kolbe electrolysis for biomass valorization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"71 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703267","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

Confinement of Atomically Dispersed Ptδ+ Sites in Zinc-Incorporated Silicalite-1 Zeolite for Enhanced Propane Dehydrogenation

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-26 DOI: 10.1021/acscatal.4c07883

Jindong Ji, Guoli Fan, Lirong Zheng, Feng Li

{"title":"Confinement of Atomically Dispersed Ptδ+ Sites in Zinc-Incorporated Silicalite-1 Zeolite for Enhanced Propane Dehydrogenation","authors":"Jindong Ji, Guoli Fan, Lirong Zheng, Feng Li","doi":"10.1021/acscatal.4c07883","DOIUrl":"https://doi.org/10.1021/acscatal.4c07883","url":null,"abstract":"For industrial use, propylene production requires efficient and cost-effective propane dehydrogenation (PDH) catalysts. Given the scarcity of platinum and toxicity of chromium, enhancing the catalytic activity and high-temperature stability of zinc-based alternative catalysts bearing a limited amount of Pt would be ideal. Here, we successfully created a low-loaded platinum-confined and zinc-incorporated MFI-type silicalite-1 zeolite catalyst via a facile one-pot synthesis route aided by a micro-liquid film reactor. It was demonstrated that highly dispersed Zn ions were fully incorporated into the S-1 framework, while atomically dispersed Ptδ+ binding to the framework oxygen atoms could be firmly confined in the S-1 micropores. The as-constructed catalyst with only 0.041 wt % Pt loading displayed an impressively ultralow deactivation rate constant of approximately 0.0007 h–1 in the PDH at the WHSV of 2.4 h–1 and 600 °C. More significantly, the catalyst achieved a remarkably high propylene production rate of 188.1 molC3H6·gPt–1·h–1 at the higher WHSV of 12 h–1, far surpassing those of the state-of-the-art PtZn- and PtSn-based catalysts for PDH operated at the medium WHSV values. By combining the multiple characterizations and density functional theory calculations, it was unveiled that the high catalytic efficiency and high-temperature stability of the catalyst was ascribed to the formation of unique atomically dispersed Ptδ+–O–Zn structures in the catalyst. This work proposes an effective strategy for tuning the nature of active metal sites in zeolites to create high-performance catalysts across diverse heterogeneous catalytic processes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703276","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