ACS Catalysis 最新文献

{"title":"Bacterial Biosynthesis of Nitrile-Containing Natural Products: Basis for Recognition of Diversified Substrates","authors":"Ming Peng, Qiaoling Wu, Lele Ma, Zhao-Jie Teng, Xuben Hou, Hongjie Zhu, Jianhua Ju","doi":"10.1021/acscatal.4c06581","DOIUrl":"https://doi.org/10.1021/acscatal.4c06581","url":null,"abstract":"Nitrile-containing natural products, despite being a limited group of secondary metabolites, display remarkable structural and functional diversities. Aldoxime formation represents a crucial step in nitrile installation via the aldoxime-nitrile pathway although structural information regarding aldoxime formation is extremely limited. Here, we report the isolation of a nitrile compound 6-dimethylallylindole-3-acetonitrile (6-DMAIAN) and identify the aldoxime-forming enzyme gene <i>diatB</i> as a robust reporter for bacterial nitrile biosynthesis. We characterize the flavin-dependent monooxygenase DiatB and provide structural and mechanistic insights into the structural parameters dictating its substrate compatibilites. This enzyme initiates a nucleophilic attack on the amino group of the substrate 6-dimethylallyl-<span>l</span>-tryptophan (6-DMAT), resulting in formation of a transient aldoxime that precedes nitrile installation. Moreover, the DiatB recognition motif is elucidated shedding light on its substrate flexibility. We also apply bioinformatics analysis to examine the distribution and diversity of functional DiatB homologues across an array of potential nitrile-forming organisms. Given the activity of DiatB and its prevalence in secondary metabolite biosynthesis, our results provide important insight into what is, arguably, the most crucial and pivotal step in nitrile biosynthesis; these findings also suggest a promising enzymatic tool for nitrile drug design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"70 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142645847","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}

{"title":"Unraveling the Key Factors on Structure–Property–Activity Correlations for Photocatalytic Hydrogen Production of Covalent Organic Frameworks","authors":"Pengyu Dong, Cunxia Wang, Lihua Zhang, Jinkang Pan, Boyuan Zhang, Jinlong Zhang","doi":"10.1021/acscatal.4c04968","DOIUrl":"https://doi.org/10.1021/acscatal.4c04968","url":null,"abstract":"It has been a challenging task to clearly elucidate various structural features and how their interactions affect the photocatalytic hydrogen production performance. In this work, various factors, including crystallinity, specific surface area associated with morphology, energy band gap and energy levels, surface charge, and hydrophilicity, were employed to investigate the structure–property–activity correlations of β-ketoenamine-linked covalent organic framework (TpPa-1-COF) for photocatalytic H₂ production, which could influence the light harvesting, charge separation and transfer, and surface catalytic active sites. By using different methods to prepare TpPa-1-COFs, we can regulate these influencing factors to investigate their relationship with activity. It is found that the TpPa-1-COF prepared by a molecular organization method (labeled as TpPa-1 (MO)) exhibits the highest photocatalytic H₂ evolution activity compared with the TpPa-1-COF samples prepared by solvothermal methods using acetic acid (HOAc) as a catalyst (TpPa-1 (ST-HOAc)) and KOH solution as a catalyst (TpPa-1 (ST-KOH)), which is associated with the highest crystallinity, the optimal energy levels, the largest BET-specific surface area, and the best hydrophilicity for TpPa-1 (MO). Moreover, our findings suggest that the enhanced total photocatalytic H₂ evolution efficiency (η_total) of TpPa-1 (MO) may be mainly attributed to the efficient separation and migration of photogenerated charges (η₂) and the vibrant surface catalytic active sites (η₃). Overall, this work provides some deep insights into the structure–property–activity relation of TpPa-1-COF photocatalysts, which offers valuable inspiration and guidance for the thoughtful design of COF-based photocatalysts for H₂ evolution.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665252","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}

{"title":"Activation of Lattice Oxygen in Nitrogen-Doped High-Entropy Oxide Nanosheets for Highly Efficient Oxygen Evolution Reaction","authors":"Shengqin Guan, Baoen Xu, Xingbo Yu, Yonghong Ye, Yuting Liu, Taotao Guan, Yu Yang, Jiali Gao, Kaixi Li, Jianlong Wang","doi":"10.1021/acscatal.4c05997","DOIUrl":"https://doi.org/10.1021/acscatal.4c05997","url":null,"abstract":"High-entropy oxides (HEOs) are potential electrocatalysts for overcoming the sluggish kinetics of the oxygen evolution reaction (OER). Conventionally, the thermodynamic barrier of the lattice oxygen mechanism (LOM) is lower than that of the adsorbate evolution mechanism (AEM). However, controlling the transition from the AEM to the LOM remains challenging. Herein, an in situ modulation strategy has been developed to synthesize N-FeCoNiAlMoO_<i>x</i> by introducing structural directing agents and electronic modulators. Different instruments were used to identify the nitridation-triggered micromorphologies and phase transformations. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS) reveal the optimized electronic structures after nitrogen doping. N-FeCoNiAlMo_<i>x</i> exhibits OER performance with low overpotentials of 240 and 285 mV at 10 and 100 mA·cm^–2, respectively. pH dependence, free-radical capture experiments, and density functional theory (DFT) calculations confirm that nitrogen doping facilitates the LOM pathway. This work elucidates nitrogen’s critical role and the LOM pathway’s contribution to efficient OER performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665253","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}

{"title":"Thermochemical Correlations of Redox and Brønsted Sites on Bifunctional Polyoxometalate Clusters and Their Kinetic Consequences in Methanol-O2 Catalysis","authors":"Guangming Cai, Ya-Huei Cathy Chin","doi":"10.1021/acscatal.4c04745","DOIUrl":"https://doi.org/10.1021/acscatal.4c04745","url":null,"abstract":"Kinetic interconnectivities of methanol oxidative dehydrogenation and dehydration are manifestation of the underlying thermochemical/electronic correlations between redox and Brønsted sites on bifunctional Keggin-type polyoxometalate (POM) phosphomolybdic acid clusters with their electronic properties perturbed by sodium cation exchange (H<i>_x</i>Na_3–<i>x</i>PMo, <i>x</i> = 3–0). As sodium exchange increases, activation free energies for the elementary C–H scission in methanol oxidative dehydrogenation, occurring at isolated redox sites (O*) or Brønsted acid-redox site pairs (OH/O*), and for the first-order C–O formation in methanol dehydration, occurring at Brønsted sites, increase proportionally within 10–11 kJ mol^–1 at 433 K, while their activation enthalpies exhibit an inverse correlation. A Born–Haber thermochemical analysis reveals the reasons behind the site interconnectivities by establishing their respective kinetic-thermochemical relationships. The kinetically relevant C–H scission involves a late transition state, either [HOCH₂···H···O*]^‡ at O* or [OH···HOCH₂···H···O*]^‡ at OH/O*, with the transfer of an electron (e^–) and a proton (H⁺) as an H atom (H•) from the methyl fragment to redox sites, where hydrogen addition energy (HAE), comprising the negative electron affinity (−<i>EA</i>_POM) and proton affinity (−PA) of POM clusters, is a kinetic descriptor. The parallel methanol C–O formation features a late carbocationic transition state, [(CH₃OH···CH₃⁺···H₂O)···POM^–]^‡, involving proton transfer from POM clusters to adsorbed methanol species, where the deprotonation energy (DPE) of the Brønsted site serves as a kinetic descriptor. Notably, hydrogen addition energy decreases by ∼23 kJ mol^–1, while deprotonation energy increases by 80–230 kJ mol^–1, as sodium exchange increases. This slight negative thermochemical correlation arises from the inherent opposing proton transfers during redox (−PA) and Brønsted acid catalysis (DPE), modulated by the energetic effect of electron transfer (−<i>EA</i>_POM) upon sodium exchange on H<i>_x</i>Na_3–<i>x</i>PMo clusters (<i>x</i> = 3–1). The mechanistic interpretation and framework established here explicitly correlate the kinetic, thermochemical, and electronic properties of redox and Brønsted sites, offering insights into their intrinsic reactivity couplings, and are applicable to other bifunctional catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642976","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}

{"title":"Effect of Cation and Anion Vacancies in Ruthenium Oxide on the Activity and Stability of Acidic Oxygen Evolution","authors":"Jiao Yang, Keyu An, Zhichao Yu, Lulu Qiao, Youpeng Cao, Yujuan Zhuang, Chunfa Liu, Lun Li, Lishan Peng, Hui Pan","doi":"10.1021/acscatal.4c02779","DOIUrl":"https://doi.org/10.1021/acscatal.4c02779","url":null,"abstract":"Electrocatalysts capable of working efficiently in acidic media for the oxygen evolution reaction (OER) are highly demanded for the large-scale utilization of proton exchange membrane (PEM) water electrolysis. This study focuses on the design and fabrication of cation/oxygen vacancy-enriched RuO₂ catalysts to investigate the impact of defect types on the OER activity and stability of RuO₂. The comprehensive blend of experimental and theoretical approaches elucidates that the presence of Ru vacancies in Ru_1–<i>x</i>O₂ modulates the d-band center and optimizes the adsorption energy of the OER intermediates, thereby augmenting the intrinsic OER activity. Conversely, the presence of oxygen vacancies in RuO_2-x diminishes the strength of Ru–O bonds, suppressing the involvement of the lattice oxygen oxidation mechanism (LOM) and Ru dissolution, consequently enhancing long-term stability. Notably, Ru_1–<i>x</i>O₂ exhibits the lowest overpotential of 212 mV at 10 mA cm_geo^–2, while RuO_2–<i>x</i> demonstrates superior stability, enduring 400 h under 10 mA cm_geo^–2, surpassing many catalysts for acidic OER in the literature. Our findings demonstrate that defect engineering is a promising strategy to achieve electrocatalysts with super catalytic performance in acid media for water electrolysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642600","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}

{"title":"Computational Design-Enabled Divergent Modification of Monoterpene Synthases for Terpenoid Hyperproduction","authors":"Liqiu Su, Pi Liu, Weidong Liu, Qi Liu, Jian Gao, Quanlu Zhao, Kaizhi Jia, Xiang Sheng, Hongwu Ma, Qinhong Wang, Zongjie Dai","doi":"10.1021/acscatal.4c05863","DOIUrl":"https://doi.org/10.1021/acscatal.4c05863","url":null,"abstract":"Enzymes’ catalytic promiscuity enables the alteration of product specificity via protein engineering; yet, harnessing this promiscuity to achieve desired catalytic reactions remains challenging. Here, we identified HCinS, a monoterpene synthase (MTPS) with a high efficiency and specificity for 1,8-cineole biosynthesis. Quantum mechanics/molecular mechanics (QM/MM) simulations, which were performed based on the resolved crystal structure of HCinS, revealed the mechanistic details of the biosynthetic cascade reactions. Guided by these insights, <i>in silico</i> HCinS variants were designed with fine-tuned transition-state energies and reaction microenvironments. Three variants (T111A, N135H, F236M), each with one amino acid substitution, exhibited high specificity in the production of monocyclic (<i>R</i>)-α-terpineol, (<i>R</i>)-limonene, and acyclic myrcene, respectively, maintaining over 55% efficiency of native HCinS. These designed HCinS variants surpassed naturally evolved isozymes in catalytic capacity and enabled yeast to achieve the highest microbial titer of each corresponding terpene. Furthermore, the single mutation of four functional equivalent amino acids in other four identified TPSs, respectively, resulted in the expected shifts on product specificity as HCinS variants. This research offers insights into the mechanisms controlling the TPS’s product promiscuity and highlights the universal applicability of computational design in reshaping the product specificity of TPSs, thereby paving innovative avenues for creating enzymes with applications in chemistry and synthetic biology.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642604","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}

{"title":"Dual N-Heterocyclic Carbene/Photoredox-Catalyzed Coupling of Acyl Fluorides and Alkyl Silanes","authors":"Michael Jakob, Luca Steiner, Marius Göbel, Jan P. Götze, Matthew N. Hopkinson","doi":"10.1021/acscatal.4c03103","DOIUrl":"https://doi.org/10.1021/acscatal.4c03103","url":null,"abstract":"The combination of N-heterocyclic carbene (NHC) organocatalysis with photochemical activation is becoming increasingly established as an approach for conducting radical organic reactions under mild and practical conditions. As comparatively easy to prepare and handle organic compounds, alkyl silanes are attractive substrates for radical chemistry as desilylative mesolysis of the corresponding radical cations is known to be rapid. Here, we report the successful application of benzyl silane derivatives as source of alkyl radicals in dual NHC/photoredox-catalyzed radical–radical coupling reactions with acyl fluorides. Relatively electron-rich benzyl silanes reacted smoothly to afford the corresponding ketones in generally good yields, while optimization of the NHC and photocatalyst allowed for a wider scope including primary benzyl substrates. Furthermore, initial experiments revealed that organosilanes bearing N-, O- and S-heteroatoms can also serve as alkyl radical sources under these conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637502","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}

{"title":"Manganese-Catalyzed Asymmetric Hydrogenation for Atroposelective Dynamic Kinetic Resolution of Heterobiaryl Ketone N-Oxides","authors":"Yin-Bo Wan, Xiang-Ping Hu","doi":"10.1021/acscatal.4c04979","DOIUrl":"https://doi.org/10.1021/acscatal.4c04979","url":null,"abstract":"An atroposelective dynamic kinetic resolution of configurationally labile heterobiaryl ketone <i>N</i>-oxides via Mn-catalyzed asymmetric hydrogenation has been disclosed. By use of a structurally finely tuned chiral ferrocenyl P,N,N-ligand, the hydrogenation proceeds smoothly under mild conditions with simultaneous installation of central and axial chirality, giving a wide range of atropisomeric 1-arylisoquinoline and 2-arylpyridine <i>N</i>-oxides bearing a chiral alcohol structure with high diastereo- and enantioselectivities. The diastereomer of the hydrogenation product could be readily prepared in a stereospecific way with the complete inversion of the central chirality via Mitsunobu reaction. The value of this central- and axial-chiral heterobiaryl <i>N</i>-oxide scaffold is preliminarily demonstrated by its successful utility as a chiral catalyst in asymmetric allylation of benzaldehyde with allyltrichlorosilane.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637498","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}

{"title":"Enhanced Photocatalytic Production of Hydrogen Peroxide by Covalent Triazine Frameworks with Stepwise Electron Transfer","authors":"Hao Zhang, Wenxin Wei, Kai Chi, Yong Zheng, Xin Ying Kong, Liqun Ye, Yan Zhao, Kai A. I. Zhang","doi":"10.1021/acscatal.4c05328","DOIUrl":"https://doi.org/10.1021/acscatal.4c05328","url":null,"abstract":"The photosynthesis of hydrogen peroxide (H₂O₂) from pure water and oxygen using metal-free photocatalysts offers a renewable approach to convert solar energy to storable chemical energy. However, the efficiency of H₂O₂ photosynthesis is often hindered by the rapid recombination of photogenerated charge carriers. Herein, we present an elegantly designed covalent triazine framework (CTF) photocatalyst, denoted as Ace-asy-CTF, with a stepwise electron transfer pathway for the highly efficient photosynthesis of H₂O₂. Notably, Ace-asy-CTF possesses localized excited-state charge distribution and stepwise electron transfer that is created by the weakly conjugated acetenyl units in the asymmetric frameworks, as revealed by transient spectroscopies and further supported by theoretical calculations. Meanwhile, the introduced acetenyl units also serve as active sites for the oxygen reduction reaction (ORR). The simultaneously enhanced stepwise charge transfer and two-step 2e^– ORR in Ace-asy-CTF result in an excellent H₂O₂ yield of 2594 μmol g^–1 h^–1, directly produced from oxygen and pure water without requiring any sacrificial reagents. This work paves the way for the development of next-generation metal-free catalysts, providing a feasible benchmark for the highly efficient and stable photosynthesis of H₂O₂.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"25 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637858","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}

{"title":"Electrochemical Insights into Hydrogen Peroxide Generation on Carbon Electrodes: Influence of Defects, Oxygen Functional Groups, and Alkali Metals in the Electrolyte","authors":"André Olean-Oliveira, Najeeb Hasnain, Ricardo Martínez-Hincapié, Ulrich Hagemann, Adarsh Jain, Doris Segets, Ioannis Spanos, Viktor Čolić","doi":"10.1021/acscatal.4c04734","DOIUrl":"https://doi.org/10.1021/acscatal.4c04734","url":null,"abstract":"Hydrogen peroxide (H₂O₂) is an environmentally friendly oxidant, with production reaching 5.7 million tons by 2028 and a market size of USD 4.04 billion by 2029. Understanding the mechanism of oxygen reduction to H₂O₂ and the structure–activity relations on carbon materials is, therefore, of high significance for the more environmentally friendly synthesis of this important chemical. We have used oriented pyrolytic graphite (PG-edge and PG-basal) and glassy carbon (GC) as model electrodes to investigate the influence of carbon defects, oxygen-containing functional groups, and the presence of alkali metals on the activity and selectivity toward H₂O₂ production under acidic conditions. Electrochemical measurements, such as rotating ring disk electrode and electrochemical impedance spectroscopy, as well as in situ Raman spectroelectrochemistry indicated that PG-basal and GC electrodes preferentially form H₂O₂ as the product through the two-electron pathway via inner and outer sphere mechanisms, respectively. The mechanism is significantly affected by the potential of maximal entropy, which determines the position of species in the solution within the inner or outer Helmholtz plane. The influence of alkali cations (Li⁺, Na⁺, K⁺, and Cs⁺) on the oxygen reduction reaction of these model carbon electrodes was investigated. Large cations, e.g., K⁺ and Cs⁺, showed influence on the reaction intermediates and thus on the electrodes’ selectivity. The present study provides important insights and contributions to the fundamental aspects of hydrogen peroxide production in acidic conditions and further advancements in the development of metal-free carbon-based catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"247 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642602","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}