The P450 monooxygenase TleB (CYP107E48) catalyzes intramolecular C–S bond formation in a thiol-containing substrate, yielding two sulfur-containing indolactam derivatives (P1 and P2). However, the key sites influencing TleB’s product selectivity and the molecular mechanisms underlying the selective C–S bond formation are not fully understood. To address this, we created an artificial self-sufficient P450, TleB-CYP116B46, by fusing TleB with the reductase domain of CYP116B46. Structure-guided engineering of TleB-CYP116B46 generates variant L85G with 99% selectivity for P1 and variant I282L/Q387L/I234F with 95% selectivity for P2. Exploring TleB homologues and generating corresponding mutants elucidate the identified sites’ crucial role in product selectivity. Computational studies suggest a diradical mechanism for C–S bond formation for both P1 and P2 products. Intriguingly, we found that the substrate radical could undergo conformational changes in both the S–H and indole groups. The L85G variant facilitates the conformational switch of the indole radical group, thereby leading to the selective C–S bond formation for the P1 product. By contrast, the I282L/Q387L/I234F variant barricades the conformational switch of the indole radical group, affording the P2 product. Our simulations highlight that the protein environment can dictate the dynamics and positioning of the substrate radical, thereby leading to the selective C–S bond formation in P450s.
{"title":"Mechanistic Insights into the Selective C–S Bond Formation by P450 TleB","authors":"Hongxun Gao, Yakun Fan, Xuwei He, Xiaogang Peng, Zhen Li, Yanxin Zheng, Shengbiao Ji, Longwu Ye, Aitao Li, Binju Wang, Jing Zhao","doi":"10.1021/acscatal.4c03328","DOIUrl":"https://doi.org/10.1021/acscatal.4c03328","url":null,"abstract":"The P450 monooxygenase TleB (CYP107E48) catalyzes intramolecular C–S bond formation in a thiol-containing substrate, yielding two sulfur-containing indolactam derivatives (P1 and P2). However, the key sites influencing TleB’s product selectivity and the molecular mechanisms underlying the selective C–S bond formation are not fully understood. To address this, we created an artificial self-sufficient P450, TleB-CYP116B46, by fusing TleB with the reductase domain of CYP116B46. Structure-guided engineering of TleB-CYP116B46 generates variant L85G with 99% selectivity for P1 and variant I282L/Q387L/I234F with 95% selectivity for P2. Exploring TleB homologues and generating corresponding mutants elucidate the identified sites’ crucial role in product selectivity. Computational studies suggest a diradical mechanism for C–S bond formation for both P1 and P2 products. Intriguingly, we found that the substrate radical could undergo conformational changes in both the S–H and indole groups. The L85G variant facilitates the conformational switch of the indole radical group, thereby leading to the selective C–S bond formation for the P1 product. By contrast, the I282L/Q387L/I234F variant barricades the conformational switch of the indole radical group, affording the P2 product. Our simulations highlight that the protein environment can dictate the dynamics and positioning of the substrate radical, thereby leading to the selective C–S bond formation in P450s.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489719","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}
Spiro-oxazolidinones are highly valuable compounds in the fields of medicinal and organic chemistry; however, the methods for synthesizing these compounds have not been well established. Herein, we present a biocatalytic methodology for the construction of spiro-oxazolidinones through the halohydrin dehalogenase-catalyzed ring expansion of spiro-epoxides. By performing screening and protein engineering of halohydrin dehalogenases, both chiral and racemic spiro-oxazolidinones were synthesized in 24–47% yields (90–98% ee) and 69–98% yields, respectively. The biocatalytic method was also applied to the efficient synthesis of the drug fenspiride at a high substrate concentration of 200 mM (44 g/L). In addition, a chemo-enzymatic strategy was proposed to overcome the limitation of the maximum 50% yield inherent in the kinetic resolution process. Moreover, large-scale synthesis and representative transformations of the spiro-oxazolidinones were carried out to provide additional evidence of the practicality and applicability of the biocatalytic approach.
{"title":"Biocatalytic Construction of Spiro-Oxazolidinones via Halohydrin Dehalogenase-Catalyzed Ring Expansion of Spiro-Epoxides","authors":"Jin-Mei Ma, Yuan-Fei Wang, Run-Ping Miao, Xiao Jin, Hui-Hui Wang, Yong-Zheng Chen, Nan-Wei Wan","doi":"10.1021/acscatal.4c02122","DOIUrl":"https://doi.org/10.1021/acscatal.4c02122","url":null,"abstract":"Spiro-oxazolidinones are highly valuable compounds in the fields of medicinal and organic chemistry; however, the methods for synthesizing these compounds have not been well established. Herein, we present a biocatalytic methodology for the construction of spiro-oxazolidinones through the halohydrin dehalogenase-catalyzed ring expansion of spiro-epoxides. By performing screening and protein engineering of halohydrin dehalogenases, both chiral and racemic spiro-oxazolidinones were synthesized in 24–47% yields (90–98% <i>ee</i>) and 69–98% yields, respectively. The biocatalytic method was also applied to the efficient synthesis of the drug fenspiride at a high substrate concentration of 200 mM (44 g/L). In addition, a chemo-enzymatic strategy was proposed to overcome the limitation of the maximum 50% yield inherent in the kinetic resolution process. Moreover, large-scale synthesis and representative transformations of the spiro-oxazolidinones were carried out to provide additional evidence of the practicality and applicability of the biocatalytic approach.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489783","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}
Pub Date : 2024-06-30DOI: 10.1021/acscatal.4c02690
Jiujun Deng, Guoqing Li, Duan Yan, Wei Zhang, Kun Feng, Kaiqi Nie, Changhai Liu, Xiaoxin Lv, Jun Zhong
High-temperature sintering is critical for efficient hematite photoanodes in terms of improving the crystallinity and minimizing deficiencies. However, prolonged conventional furnace annealing requires high energy consumption and simultaneously results in serious damage to the transparent conducting oxide (TCO) substrate. This work demonstrates a universal wet-interfacial Joule heating strategy for rapidly synthesizing high-performance metastable protohematite photoanodes, which greatly decreases the power consumption and causes less damage to the TCO substrate by shortening the sintering time to ∼90 s. More importantly, the protohematite phase was found to effectively facilitate the charge dynamics in the bulk and surface of the as-resulting photoanode by increasing donor density and lowering the oxygen evolution reaction overpotential via offering dual active sites (lattice oxygen and Fe sites). Moreover, this annealing strategy could be well coupled with commonly used Ti-treatment to achieve a further performance enhancement and also shows high feasibility in rapidly fabricating efficient TiO2 and BiVO4 photoanodes. This study opens a facile, rapid, and reliable approach for fabricating efficient metal oxide photoanodes, contributing to the development of photoelectrochemical water splitting.
{"title":"Programmable Wet-Interfacial Joule Heating to Rapidly Synthesize Metastable Protohematite Photoanodes: Metal and Lattice Oxygen Dual Sites for Improving Water Oxidation","authors":"Jiujun Deng, Guoqing Li, Duan Yan, Wei Zhang, Kun Feng, Kaiqi Nie, Changhai Liu, Xiaoxin Lv, Jun Zhong","doi":"10.1021/acscatal.4c02690","DOIUrl":"https://doi.org/10.1021/acscatal.4c02690","url":null,"abstract":"High-temperature sintering is critical for efficient hematite photoanodes in terms of improving the crystallinity and minimizing deficiencies. However, prolonged conventional furnace annealing requires high energy consumption and simultaneously results in serious damage to the transparent conducting oxide (TCO) substrate. This work demonstrates a universal wet-interfacial Joule heating strategy for rapidly synthesizing high-performance metastable protohematite photoanodes, which greatly decreases the power consumption and causes less damage to the TCO substrate by shortening the sintering time to ∼90 s. More importantly, the protohematite phase was found to effectively facilitate the charge dynamics in the bulk and surface of the as-resulting photoanode by increasing donor density and lowering the oxygen evolution reaction overpotential via offering dual active sites (lattice oxygen and Fe sites). Moreover, this annealing strategy could be well coupled with commonly used Ti-treatment to achieve a further performance enhancement and also shows high feasibility in rapidly fabricating efficient TiO<sub>2</sub> and BiVO<sub>4</sub> photoanodes. This study opens a facile, rapid, and reliable approach for fabricating efficient metal oxide photoanodes, contributing to the development of photoelectrochemical water splitting.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489800","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}
Pub Date : 2024-06-28DOI: 10.1021/acscatal.4c00675
Tareq Al-Attas, Karthick Kannimuthu, Mohd Adnan Khan, Md Golam Kibria
The electrochemical partial oxidation of methane (CH4) to value-added chemicals under ambient conditions provides a solution for harnessing abundant natural gas resources. Here, we investigate α-Fe2O3 as a model catalyst to gain a mechanistic understanding of the electrochemical CH4 oxidation reaction (eCH4OR). During chronoamperometric experiments, we obtain liquid products (formic acid, acetic acid, and acetone) with ∼6.5% total Faradaic efficiency at 2.3 V versus the reversible hydrogen electrode (VRHE). At lower potentials below 2.0 VRHE, non-Faradaic CH4 adsorption occurred, confirmed by in situ ATR-SEIRAS (attenuated total reflectance–surface-enhanced infrared absorption spectroscopy) and impedance spectroscopies. In addition to verifying the presence of the FeIVO species, in situ spectroelectrochemical measurements revealed that CH4 oxidation initiates via H-abstraction to form •OCH3 species. The reaction undergoes further oxidation steps, leading to formate. Coupling between •OCH3 and formate generates •OCOCH3 species. Further, C–C coupling between – COCH3 and – CH3 resulted in acetone formation. Real-time proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS) confirms the proposed pathways. Based on these observations, we propose a mechanistic pathway for selective CH4 electrooxidation.
{"title":"Uncovering Electrochemical Methane Oxidation Mechanism through the In Situ Detection of Reaction Intermediates","authors":"Tareq Al-Attas, Karthick Kannimuthu, Mohd Adnan Khan, Md Golam Kibria","doi":"10.1021/acscatal.4c00675","DOIUrl":"https://doi.org/10.1021/acscatal.4c00675","url":null,"abstract":"The electrochemical partial oxidation of methane (CH<sub>4</sub>) to value-added chemicals under ambient conditions provides a solution for harnessing abundant natural gas resources. Here, we investigate α-Fe<sub>2</sub>O<sub>3</sub> as a model catalyst to gain a mechanistic understanding of the electrochemical CH<sub>4</sub> oxidation reaction (eCH<sub>4</sub>OR). During chronoamperometric experiments, we obtain liquid products (formic acid, acetic acid, and acetone) with ∼6.5% total Faradaic efficiency at 2.3 V versus the reversible hydrogen electrode (V<sub>RHE</sub>). At lower potentials below 2.0 V<sub>RHE</sub>, non-Faradaic CH<sub>4</sub> adsorption occurred, confirmed by in situ ATR-SEIRAS (attenuated total reflectance–surface-enhanced infrared absorption spectroscopy) and impedance spectroscopies. In addition to verifying the presence of the Fe<sup>IV</sup>O species, in situ spectroelectrochemical measurements revealed that CH<sub>4</sub> oxidation initiates via H-abstraction to form •OCH<sub>3</sub> species. The reaction undergoes further oxidation steps, leading to formate. Coupling between •OCH<sub>3</sub> and formate generates •OCOCH<sub>3</sub> species. Further, C–C coupling between – COCH<sub>3</sub> and – CH<sub>3</sub> resulted in acetone formation. Real-time proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS) confirms the proposed pathways. Based on these observations, we propose a mechanistic pathway for selective CH<sub>4</sub> electrooxidation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463695","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}
Perovskite-type CaTaO2N has a band structure suitable for one-step-excitation overall photocatalytic water splitting under visible light. However, the poor electron–hole separation characteristics of this material limit its water splitting activity. In the present work, N-enriched CaTaO2N was prepared by sequential nitridation in the presence and then the absence of a flux. The nitride-enriched CaTaO2N was found to promote one-step-excitation overall water splitting efficiently and evolved H2 and O2 stoichiometrically under visible light with an apparent quantum efficiency of 0.45% at 420 nm. This is the highest value yet reported for a CaTaO2N-based material applied to overall water splitting. The increased activity of this photocatalyst is attributed to the incorporation of nitride ions, which enhanced the separation of photogenerated electrons and holes. This study suggests a promising approach to boosting one-step-excitation overall photocatalytic water splitting, using nitride ion enrichment as a means of manipulating charge transfer behavior.
{"title":"Enhancing the Photocatalytic Activity of CaTaO2N for Overall Water Splitting through Surface Nitride Ion Enrichment","authors":"Xuecheng Liu, Linjie Yan, Wenpeng Li, Kaihong Chen, Faze Wang, Jiadong Xiao, Takashi Hisatomi, Tsuyoshi Takata, Kazunari Domen","doi":"10.1021/acscatal.4c01590","DOIUrl":"https://doi.org/10.1021/acscatal.4c01590","url":null,"abstract":"Perovskite-type CaTaO<sub>2</sub>N has a band structure suitable for one-step-excitation overall photocatalytic water splitting under visible light. However, the poor electron–hole separation characteristics of this material limit its water splitting activity. In the present work, N-enriched CaTaO<sub>2</sub>N was prepared by sequential nitridation in the presence and then the absence of a flux. The nitride-enriched CaTaO<sub>2</sub>N was found to promote one-step-excitation overall water splitting efficiently and evolved H<sub>2</sub> and O<sub>2</sub> stoichiometrically under visible light with an apparent quantum efficiency of 0.45% at 420 nm. This is the highest value yet reported for a CaTaO<sub>2</sub>N-based material applied to overall water splitting. The increased activity of this photocatalyst is attributed to the incorporation of nitride ions, which enhanced the separation of photogenerated electrons and holes. This study suggests a promising approach to boosting one-step-excitation overall photocatalytic water splitting, using nitride ion enrichment as a means of manipulating charge transfer behavior.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463525","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}
Pub Date : 2024-06-28DOI: 10.1021/acscatal.4c03019
Pavel S. Kulyabin, Oxana V. Magdysyuk, Aaron B. Naden, Daniel M. Dawson, Ketan Pancholi, Matthew Walker, Massimo Vassalli, Amit Kumar
We report here a method of making polyketones from the coupling of diketones and diols using a manganese pincer complex. The methodology allows us to access various polyketones (polyarylalkylketone) containing aryl, alkyl, and ether functionalities, bridging the gap between the two classes of commercially available polyketones: aliphatic polyketones and polyaryletherketones. Using this methodology, 12 polyketones have been synthesized and characterized using various analytical techniques to understand their chemical, physical, morphological, and mechanical properties. Based on previous reports and our studies, we suggest that the polymerization occurs via a hydrogen-borrowing mechanism that involves the dehydrogenation of diols to dialdehyde followed by aldol condensation of dialdehyde with diketones to form chalcone derivatives and their subsequent hydrogenation to form polyarylalkylketones.
{"title":"Manganese-Catalyzed Synthesis of Polyketones Using Hydrogen-Borrowing Approach","authors":"Pavel S. Kulyabin, Oxana V. Magdysyuk, Aaron B. Naden, Daniel M. Dawson, Ketan Pancholi, Matthew Walker, Massimo Vassalli, Amit Kumar","doi":"10.1021/acscatal.4c03019","DOIUrl":"https://doi.org/10.1021/acscatal.4c03019","url":null,"abstract":"We report here a method of making polyketones from the coupling of diketones and diols using a manganese pincer complex. The methodology allows us to access various polyketones (polyarylalkylketone) containing aryl, alkyl, and ether functionalities, bridging the gap between the two classes of commercially available polyketones: aliphatic polyketones and polyaryletherketones. Using this methodology, 12 polyketones have been synthesized and characterized using various analytical techniques to understand their chemical, physical, morphological, and mechanical properties. Based on previous reports and our studies, we suggest that the polymerization occurs via a hydrogen-borrowing mechanism that involves the dehydrogenation of diols to dialdehyde followed by aldol condensation of dialdehyde with diketones to form chalcone derivatives and their subsequent hydrogenation to form polyarylalkylketones.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463674","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}
Pub Date : 2024-06-28DOI: 10.1021/acscatal.4c01369
Rui Yu, Zhaorui Liu, Dominik Legut, Junwei Sun, Qianfan Zhang, Joseph S. Francisco, Ruifeng Zhang
The electrocatalytic synthesis of NH3 holds immense significance for energy conservation in industrial and agricultural production. Herein, an efficient solution is proposed for MXene-based high-activity nitrogen reduction reaction (NRR) catalysts that are modified using tetranuclear non-noble 3d transition metal clusters (M4). The thorough exploration of M4/Ti2CO2 candidates reveals that the thermodynamically and kinetically stable Cr4/Ti2CO2 possesses the lowest overpotential (0.35 V) and high selectivity, comparable to those of well-known NRR catalysts such as Ru(0001) (0.43 V) and Au(310) (1.91 V). In addition, the doping of Fe into Cr4 clusters can further reduce the overpotential and kinetic barriers by 31 and 46%, respectively. The analysis of the complicated bonding nature reveals the mechanism of the catalytic activity, which demonstrates the role of clusters pulling π/σ electrons from N2 while simultaneously back-donating d orbital electrons to the π* orbital. A descriptor (φ), related to intrinsic transferred charges (Δe) of the cluster, is proposed to accurately determine the NRR catalytic activity using simple calculations, and the linear correlation between them can reach 0.98. This work provides guidance for designing promising cluster-modified MXene catalysts for NRR and an elucidation of the electronic factors governing catalytic activity.
{"title":"Highly Efficient and Selective Nitrogen Reduction Reaction Catalysis of Cluster-Modified MXene Nanosheets","authors":"Rui Yu, Zhaorui Liu, Dominik Legut, Junwei Sun, Qianfan Zhang, Joseph S. Francisco, Ruifeng Zhang","doi":"10.1021/acscatal.4c01369","DOIUrl":"https://doi.org/10.1021/acscatal.4c01369","url":null,"abstract":"The electrocatalytic synthesis of NH<sub>3</sub> holds immense significance for energy conservation in industrial and agricultural production. Herein, an efficient solution is proposed for MXene-based high-activity nitrogen reduction reaction (NRR) catalysts that are modified using tetranuclear non-noble 3d transition metal clusters (M<sub>4</sub>). The thorough exploration of M<sub>4</sub>/Ti<sub>2</sub>CO<sub>2</sub> candidates reveals that the thermodynamically and kinetically stable Cr<sub>4</sub>/Ti<sub>2</sub>CO<sub>2</sub> possesses the lowest overpotential (0.35 V) and high selectivity, comparable to those of well-known NRR catalysts such as Ru(0001) (0.43 V) and Au(310) (1.91 V). In addition, the doping of Fe into Cr<sub>4</sub> clusters can further reduce the overpotential and kinetic barriers by 31 and 46%, respectively. The analysis of the complicated bonding nature reveals the mechanism of the catalytic activity, which demonstrates the role of clusters pulling π/σ electrons from N<sub>2</sub> while simultaneously back-donating d orbital electrons to the π* orbital. A descriptor (φ), related to intrinsic transferred charges (Δ<i>e</i>) of the cluster, is proposed to accurately determine the NRR catalytic activity using simple calculations, and the linear correlation between them can reach 0.98. This work provides guidance for designing promising cluster-modified MXene catalysts for NRR and an elucidation of the electronic factors governing catalytic activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464046","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}
Pub Date : 2024-06-28DOI: 10.1021/acscatal.4c02557
David G. Barton, Aditya Bhan, Prashant Deshlahra, Rajamani Gounder, David Hibbitts, Beata A. Kilos, Gina Noh, Justin M. Notestein, Michele L. Sarazen, Stuart L. Soled
Enrique Iglesia is an internationally recognized leader in the field of heterogeneous catalysis. His trademark approach places a premium on kinetic and mechanistic descriptions of catalytic sequences, complemented by synthetic methods to prepare catalytic centers uniform in composition and by computational chemistry methods to adjudicate among competing hypotheses, with the aim of describing the function of catalytic active sites at the level of elementary steps in reaction mechanisms. Enrique began his independent career in industry, spending 11 years at the Exxon Corporate Research Laboratories. In 1993, he moved to academia to become a full professor in the Department of Chemical and Biomolecular Engineering at the University of California, Berkeley where he founded the Berkeley incarnation of the Laboratory for the Science and Applications of Catalysis (LSAC). In that time, he has coauthored >350 publications (with an h-index of >120) and >50 patents and has advised ∼30 Ph.D. students and ∼100 postdoctoral and visiting scholars, more than 30 of whom continue his legacy of teaching and scholarship in their own academic appointments around the world. Enrique is a member of the National Academy of Engineering, the American Academy of Arts and Sciences, the National Academy of Inventors, and the Spanish Royal Academy of Sciences, and has received numerous awards from the American Chemical Society, the American Institute of Chemical Engineers, and the Catalysis Societies of North America and Europe. In this Account, we discuss major research themes that have underpinned Enrique’s career, using examples that illustrate how his research has led to significant conceptual advances in our understanding of reactions facilitated by metals and metal oxides, of the consequences of acid strength and confinement in microporous solids, of the relevance of describing surfaces under realistic coverages for catalysis, and in disentangling the chemistry of active sites that mediate catalysis from the specific influences of the environments within which reactions proceed. These insights have allowed for the development of more precise and unifying descriptions of chemical reactivity and selectivity, including field-defining mechanistic interpretations and practical developments in the conversion of C1 molecules, acid–base and redox catalysis, hydrocarbon and oxygenate chain growth chemistries, NOx abatement, and Fischer–Tropsch synthesis across supported metals, carbides, and oxides. His work unifies some of the most enduring concepts in physical, organic, solid-state, and theoretical chemistry into surface catalysis, through deep knowledge about the fundamentals of catalysis and their translation into practical solutions. His research group chooses to study catalytic systems that are technologically relevant and often occur in complex environments, irrespective of whether such topics are in vogue at the time of inquiry, guide
{"title":"A Career in Catalysis: Enrique Iglesia","authors":"David G. Barton, Aditya Bhan, Prashant Deshlahra, Rajamani Gounder, David Hibbitts, Beata A. Kilos, Gina Noh, Justin M. Notestein, Michele L. Sarazen, Stuart L. Soled","doi":"10.1021/acscatal.4c02557","DOIUrl":"https://doi.org/10.1021/acscatal.4c02557","url":null,"abstract":"Enrique Iglesia is an internationally recognized leader in the field of heterogeneous catalysis. His trademark approach places a premium on kinetic and mechanistic descriptions of catalytic sequences, complemented by synthetic methods to prepare catalytic centers uniform in composition and by computational chemistry methods to adjudicate among competing hypotheses, with the aim of describing the function of catalytic active sites at the level of elementary steps in reaction mechanisms. Enrique began his independent career in industry, spending 11 years at the Exxon Corporate Research Laboratories. In 1993, he moved to academia to become a full professor in the Department of Chemical and Biomolecular Engineering at the University of California, Berkeley where he founded the Berkeley incarnation of the Laboratory for the Science and Applications of Catalysis (LSAC). In that time, he has coauthored >350 publications (with an h-index of >120) and >50 patents and has advised ∼30 Ph.D. students and ∼100 postdoctoral and visiting scholars, more than 30 of whom continue his legacy of teaching and scholarship in their own academic appointments around the world. Enrique is a member of the National Academy of Engineering, the American Academy of Arts and Sciences, the National Academy of Inventors, and the Spanish Royal Academy of Sciences, and has received numerous awards from the American Chemical Society, the American Institute of Chemical Engineers, and the Catalysis Societies of North America and Europe. In this Account, we discuss major research themes that have underpinned Enrique’s career, using examples that illustrate how his research has led to significant conceptual advances in our understanding of reactions facilitated by metals and metal oxides, of the consequences of acid strength and confinement in microporous solids, of the relevance of describing surfaces under realistic coverages for catalysis, and in disentangling the chemistry of active sites that mediate catalysis from the specific influences of the environments within which reactions proceed. These insights have allowed for the development of more precise and unifying descriptions of chemical reactivity and selectivity, including field-defining mechanistic interpretations and practical developments in the conversion of C<sub>1</sub> molecules, acid–base and redox catalysis, hydrocarbon and oxygenate chain growth chemistries, NO<sub><i>x</i></sub> abatement, and Fischer–Tropsch synthesis across supported metals, carbides, and oxides. His work unifies some of the most enduring concepts in physical, organic, solid-state, and theoretical chemistry into surface catalysis, through deep knowledge about the fundamentals of catalysis and their translation into practical solutions. His research group chooses to study catalytic systems that are technologically relevant and often occur in complex environments, irrespective of whether such topics are in vogue at the time of inquiry, guide","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463628","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}
Chiral vanadyl complex derived from N-salicylidene-tert-butyl-l-glycinate bearing a 3-(2,5-dimethyl)phenyl-5-bromo substituent was first tested for the catalytic feasibility of asymmetric intermolecular 1,2-alkoxy-sulfenylation of styrene with three different types of six- and five-membered ring heteroaromatic thiols in the presence of t-butyl hydroperoxide in methanol at ambient temperature. Among them, 2-mercapto-benzoxazole (BzOxz-SH) was identified as the best candidate. A variety of chiral vanadyl complexes bearing 3-aryl-5-bromo, 3,5-dihalo-, and benzo-fused salicylidene templates were further examined for optimizing yields and enantio-control. The best scenario involved the use of 5 mol % 3,5-dibromo or -dichloro catalyst at 0 °C with BzOxz-SH in MeOH. The asymmetric catalytic cross-coupling reactions proceeded smoothly with enantioselectivities of up to 94% ee of (R)-configuration by using the 3,5-dichloro catalyst for various 1° alcohols by screening through various 4-, 3-, 3,4-, 3,5-, and 2-substituted (including Me/t-Bu, Ph, OR, Cl/Br, OAc, NO2, C(O)Me, CO2Me, CN, and benzo-fused) vinylarenes. Further improvement to 96% ee was achieved by the use of 5-methyl-BzOxz-SH. The origin and catalytic mechanism of enantiocontrol through homolytic methoxy delivery to incipient benzylic radical intermediates by vanadyl-bound methoxide were proposed.
{"title":"Asymmetric Radical-Type 1,2-Alkoxy-Sulfenylation of Benzoxazole-2-Thiols to Vinylarenes Catalyzed by Chiral Vanadyl Complexes","authors":"Yueh-Hua Liu, Hao-Yang Tsui, Pei-Hsuan Chien, Chien-Tien Chen","doi":"10.1021/acscatal.4c02460","DOIUrl":"https://doi.org/10.1021/acscatal.4c02460","url":null,"abstract":"Chiral vanadyl complex derived from <i>N</i>-salicylidene-<i>tert</i>-butyl-<span>l</span>-glycinate bearing a 3-(2,5-dimethyl)phenyl-5-bromo substituent was first tested for the catalytic feasibility of asymmetric intermolecular 1,2-alkoxy-sulfenylation of styrene with three different types of six- and five-membered ring heteroaromatic thiols in the presence of <i>t</i>-butyl hydroperoxide in methanol at ambient temperature. Among them, 2-mercapto-benzoxazole (BzOxz-SH) was identified as the best candidate. A variety of chiral vanadyl complexes bearing 3-aryl-5-bromo, 3,5-dihalo-, and benzo-fused salicylidene templates were further examined for optimizing yields and enantio-control. The best scenario involved the use of 5 mol % 3,5-dibromo or -dichloro catalyst at 0 °C with BzOxz-SH in MeOH. The asymmetric catalytic cross-coupling reactions proceeded smoothly with enantioselectivities of up to 94% ee of (<i>R</i>)-configuration by using the 3,5-dichloro catalyst for various 1° alcohols by screening through various 4-, 3-, 3,4-, 3,5-, and 2-substituted (including Me/<i>t</i>-Bu, Ph, OR, Cl/Br, OAc, NO<sub>2</sub>, C(O)Me, CO<sub>2</sub>Me, CN, and benzo-fused) vinylarenes. Further improvement to 96% ee was achieved by the use of 5-methyl-BzOxz-SH. The origin and catalytic mechanism of enantiocontrol through homolytic methoxy delivery to incipient benzylic radical intermediates by vanadyl-bound methoxide were proposed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463538","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}
Pub Date : 2024-06-27DOI: 10.1021/acscatal.4c02916
Wangxin Ge, Lei Dong, Chaochen Wang, Yihua Zhu, Zhen Liu, Hongliang Jiang, Chunzhong Li
Acidic CO2 electroreduction offers a promising strategy for achieving a high CO2 utilization efficiency. However, it is highly challenging to inhibit the competing hydrogen evolution reactions (HER) due to the high concentration of protons at the electrode–electrolyte interface. The interfacial hydrogen-bond environment greatly affects proton transfer and the kinetics of hydrogen-related reactions, e.g., HER and CO2 reduction. In this work, we demonstrate that sulfonate-based electrolyte additives, including sodium p-styrenesulfonate (SPS), sodium p-toluene sulfonate (STS), and sodium benzenesulfonate (SBS), enable reconstruction of the interfacial hydrogen-bond environment and enhance the CO2 electrolysis performance. Mechanistic studies uncover that the strong hydrogen-bond interactions of these sulfonate-based additives with H2O achieve the construction of a low proton-flux interface. This leads to the suppression of proton concentration-dependent HER. The SPS-assisted acidic CO2 electrolysis yields CO with a high selectivity of 97.8% and a high single-pass carbon efficiency of 66.3% at 250 mA cm–2 on commercial Ag catalysts in acid. This work provides a facile strategy to promote acidic CO2 electrolysis by modulating the interfacial hydrogen-bond environment through electrolyte design.
酸性二氧化碳电还原为实现较高的二氧化碳利用效率提供了一种前景广阔的策略。然而，由于电极-电解质界面存在高浓度的质子，要抑制相互竞争的氢进化反应（HER）极具挑战性。界面氢键环境会极大地影响质子转移和氢相关反应的动力学，例如氢还原反应和二氧化碳还原反应。在这项工作中，我们证明了磺酸盐基电解质添加剂（包括对苯乙烯磺酸钠（SPS）、对甲苯磺酸钠（STS）和苯磺酸钠（SBS））能够重建界面氢键环境并提高二氧化碳电解性能。机理研究发现，这些磺酸盐基添加剂与 H2O 之间的强氢键相互作用实现了低质子通量界面的构建。这就抑制了质子浓度依赖性 HER。SPS 辅助酸性 CO2 电解在 250 mA cm-2 的酸性条件下，在商用银催化剂上产生 CO 的选择性高达 97.8%，单程碳效率高达 66.3%。这项研究通过电解质设计调节界面氢键环境，为促进酸性二氧化碳电解提供了一种简便的策略。
{"title":"Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO2 Electrolysis","authors":"Wangxin Ge, Lei Dong, Chaochen Wang, Yihua Zhu, Zhen Liu, Hongliang Jiang, Chunzhong Li","doi":"10.1021/acscatal.4c02916","DOIUrl":"https://doi.org/10.1021/acscatal.4c02916","url":null,"abstract":"Acidic CO<sub>2</sub> electroreduction offers a promising strategy for achieving a high CO<sub>2</sub> utilization efficiency. However, it is highly challenging to inhibit the competing hydrogen evolution reactions (HER) due to the high concentration of protons at the electrode–electrolyte interface. The interfacial hydrogen-bond environment greatly affects proton transfer and the kinetics of hydrogen-related reactions, e.g., HER and CO<sub>2</sub> reduction. In this work, we demonstrate that sulfonate-based electrolyte additives, including sodium <i>p</i>-styrenesulfonate (SPS), sodium <i>p</i>-toluene sulfonate (STS), and sodium benzenesulfonate (SBS), enable reconstruction of the interfacial hydrogen-bond environment and enhance the CO<sub>2</sub> electrolysis performance. Mechanistic studies uncover that the strong hydrogen-bond interactions of these sulfonate-based additives with H<sub>2</sub>O achieve the construction of a low proton-flux interface. This leads to the suppression of proton concentration-dependent HER. The SPS-assisted acidic CO<sub>2</sub> electrolysis yields CO with a high selectivity of 97.8% and a high single-pass carbon efficiency of 66.3% at 250 mA cm<sup>–2</sup> on commercial Ag catalysts in acid. This work provides a facile strategy to promote acidic CO<sub>2</sub> electrolysis by modulating the interfacial hydrogen-bond environment through electrolyte design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462126","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：