Chiara Zappelli, Francesco Taglieri, Silvia Schoch, Giulio Bresciani, Tiziana Funaioli, Fabio Marchetti, Stefano Zacchini, Andrea Di Giuseppe, Marcello Crucianelli
The Cover Feature represents the key intermediate in the hydroboration of a ketone promoted by a novel complex. The diiron scaffold together with the amino pendant of the hydrocarbyl ligand plays an important role in this process, with main interactions depicted as beam of lights, connecting the interacting moieties. In their Research Article, Marcello Crucianelli and co-workers present the synthesis of new diiron organometallic complexes bearing functionalities with different electronic and steric properties. A wide screening study of these molecules allowed to evaluate their catalytic activity in the hydroboration with pinacolborane, efficiently converting carbonyl compounds into organoboronates, under mild conditions. More information can be found in the Research Article by F. Marchetti, A. Di Giuseppe, M. Crucianelli, and co-workers (DOI: 10.1002/cctc.202400811).
封面特写展示了一种新型络合物在促进酮的氢硼化过程中的关键中间体。二铁支架和烃基配体的氨基垂饰在这一过程中发挥了重要作用，主要的相互作用被描绘成光束，连接着相互作用的分子。Marcello Crucianelli 及其合作者在他们的研究文章中介绍了具有不同电子和立体特性的功能性新二铁有机金属配合物的合成。通过对这些分子进行广泛的筛选研究，评估了它们在与频哪醇硼烷进行氢硼化合时的催化活性，在温和的条件下有效地将羰基化合物转化为有机硼酸盐。更多信息，请参阅 F. Marchetti、A. Di Giuseppe、M. Crucianelli 及合作者的研究文章（DOI: 10.1002/cctc.202400811）。
{"title":"Cover Feature: Multisite Amino-Allylidene Ligands from Thermal CO Elimination in Diiron Complexes and Catalytic Activity in Hydroboration Reactions (ChemCatChem 18/2024)","authors":"Chiara Zappelli, Francesco Taglieri, Silvia Schoch, Giulio Bresciani, Tiziana Funaioli, Fabio Marchetti, Stefano Zacchini, Andrea Di Giuseppe, Marcello Crucianelli","doi":"10.1002/cctc.202481802","DOIUrl":"https://doi.org/10.1002/cctc.202481802","url":null,"abstract":"<p><b>The Cover Feature</b> represents the key intermediate in the hydroboration of a ketone promoted by a novel complex. The diiron scaffold together with the amino pendant of the hydrocarbyl ligand plays an important role in this process, with main interactions depicted as beam of lights, connecting the interacting moieties. In their Research Article, Marcello Crucianelli and co-workers present the synthesis of new diiron organometallic complexes bearing functionalities with different electronic and steric properties. A wide screening study of these molecules allowed to evaluate their catalytic activity in the hydroboration with pinacolborane, efficiently converting carbonyl compounds into organoboronates, under mild conditions. More information can be found in the Research Article by F. Marchetti, A. Di Giuseppe, M. Crucianelli, and co-workers (DOI: 10.1002/cctc.202400811).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"16 18","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202481802","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142316812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Linda Klag, Roger Gläser, Ulrike Krewer, Karsten Reuter, Jan-Dierk Grunwaldt
<p>Power-to-chemical, power-to-fuel or power-to-gas are nowadays more than ever important cornerstones on the way to decarbonize the industry. The German Energy Transition (“Energiewende”)<span><sup>1-3</sup></span> aims at decreasing the net emissions of CO<sub>2</sub> by 65 % in 2030, 88 % by 2040 and CO<sub>2</sub>-neutrality in 2045.<span><sup>4</sup></span> Similar targets are set in Europe (CO<sub>2</sub>-neutrality in 2050), and other countries around the globe.</p><p>Dominant sources of renewable electricity are wind and photovoltaic solar power. In contrast to fossil resources, the availability of both renewables fluctuates on time scales of minutes to days. The necessity for a stable electricity grid posts new demands on rapid storage of large amounts of excessively generated energy – a completely new technological challenge since many ideas are still very new, immature and inefficient for application on the required technical scale. In addition, this opens new pathways to sustainable production of chemicals and brings together two areas that traditionally have only had few links: (1) solar and wind power including grids and (2) conversion to chemicals and fuels. In other words: physics, chemistry and engineering are combined to master the energy transition. At the core is catalysis which allows to transform the electrical energy and low-energy molecules such as water and CO<sub>2</sub> into high-energy reactive molecules: hydrogen, hydrocarbons and fuels. These conversions rely on electrocatalysis and (mainly) heterogeneous catalysis. Application areas in focus are water electrolysis into hydrogen and oxygen as well as conversion of CO<sub>2</sub> into hydrocarbons, especially methane, methanol, and CO.</p><p>Up to now, technical catalysis in both electrochemical and conventional chemical processes has been conducted at steady-state operation. However, these processes need to be considered under dynamic conditions that better represent the availability fluctuations of renewable power. From a scientific point of view this is very attractive, since the mechanism of catalytic processes at the molecular level is mostly unknown under transient reaction conditions.<span><sup>5-7</sup></span> New methods have to be developed that allow describing the molecular processes theoretically, understand them by <i>operando</i> spectroscopic methods and develop appropriate and adaptive catalytic materials. Hence, it requires an interdisciplinary scientific approach, involving chemistry, theoretical approaches including quantum mechanics, spectroscopy including photon science, mathematics, reactor modelling, and machine learning. New materials as well as (electro-)catalytic processes have to be predicted and then developed using a knowledge-based materials design. While this approach is promising and attractive, it also poses a challenge to the next generation of scientists, who need a deep interdisciplinary knowledge in addition to their specialized s
{"title":"Special Collection: Catalysts and Reactors under Dynamic Conditions for Energy Storage and Conversion","authors":"Linda Klag, Roger Gläser, Ulrike Krewer, Karsten Reuter, Jan-Dierk Grunwaldt","doi":"10.1002/cctc.202401191","DOIUrl":"https://doi.org/10.1002/cctc.202401191","url":null,"abstract":"<p>Power-to-chemical, power-to-fuel or power-to-gas are nowadays more than ever important cornerstones on the way to decarbonize the industry. The German Energy Transition (“Energiewende”)<span><sup>1-3</sup></span> aims at decreasing the net emissions of CO<sub>2</sub> by 65 % in 2030, 88 % by 2040 and CO<sub>2</sub>-neutrality in 2045.<span><sup>4</sup></span> Similar targets are set in Europe (CO<sub>2</sub>-neutrality in 2050), and other countries around the globe.</p><p>Dominant sources of renewable electricity are wind and photovoltaic solar power. In contrast to fossil resources, the availability of both renewables fluctuates on time scales of minutes to days. The necessity for a stable electricity grid posts new demands on rapid storage of large amounts of excessively generated energy – a completely new technological challenge since many ideas are still very new, immature and inefficient for application on the required technical scale. In addition, this opens new pathways to sustainable production of chemicals and brings together two areas that traditionally have only had few links: (1) solar and wind power including grids and (2) conversion to chemicals and fuels. In other words: physics, chemistry and engineering are combined to master the energy transition. At the core is catalysis which allows to transform the electrical energy and low-energy molecules such as water and CO<sub>2</sub> into high-energy reactive molecules: hydrogen, hydrocarbons and fuels. These conversions rely on electrocatalysis and (mainly) heterogeneous catalysis. Application areas in focus are water electrolysis into hydrogen and oxygen as well as conversion of CO<sub>2</sub> into hydrocarbons, especially methane, methanol, and CO.</p><p>Up to now, technical catalysis in both electrochemical and conventional chemical processes has been conducted at steady-state operation. However, these processes need to be considered under dynamic conditions that better represent the availability fluctuations of renewable power. From a scientific point of view this is very attractive, since the mechanism of catalytic processes at the molecular level is mostly unknown under transient reaction conditions.<span><sup>5-7</sup></span> New methods have to be developed that allow describing the molecular processes theoretically, understand them by <i>operando</i> spectroscopic methods and develop appropriate and adaptive catalytic materials. Hence, it requires an interdisciplinary scientific approach, involving chemistry, theoretical approaches including quantum mechanics, spectroscopy including photon science, mathematics, reactor modelling, and machine learning. New materials as well as (electro-)catalytic processes have to be predicted and then developed using a knowledge-based materials design. While this approach is promising and attractive, it also poses a challenge to the next generation of scientists, who need a deep interdisciplinary knowledge in addition to their specialized s","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"16 21","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202401191","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An efficient copper catalyzed fluoroalkyl-selenization reaction of olefins has been developed, providing 1,2-difluoroarylselenides in moderate to excellent yields. The readily available ethyl bromodifluoroacetate and diphenyl diselenide (Ph2Se2) have been employed as efficient radical precursor and selenization reagents to react with olefins. The reaction features a broad substrate scope, including substituted alkenes with various functional groups.
{"title":"Copper Catalyzed Fluoroalkyl-Selenization of Olefins","authors":"Jian-Liang Yu, Qing-Qing Zhang, Yi-Fan Zhang, Ya-Wen Zuo, Ruo-Xing Jin, Xi-Sheng Wang","doi":"10.1002/cctc.202401395","DOIUrl":"https://doi.org/10.1002/cctc.202401395","url":null,"abstract":"An efficient copper catalyzed fluoroalkyl-selenization reaction of olefins has been developed, providing 1,2-difluoroarylselenides in moderate to excellent yields. The readily available ethyl bromodifluoroacetate and diphenyl diselenide (Ph2Se2) have been employed as efficient radical precursor and selenization reagents to react with olefins. The reaction features a broad substrate scope, including substituted alkenes with various functional groups.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"9 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Safira Ramadhani, Quan Nguyen Dao, Yoel Imanuel, Muhammad Ridwan, Hyuntae Sohn, Hyansoo Jeong, Keunsoo Kim, Chang Won Yoon, Kwang Ho Song, Yongmin Kim
Liquid Organic Hydrogen Carriers (LOHCs) are emerging as a promising solution for global hydrogen logistics. The LOHC process involves two primary chemical reactions: hydrogenation for hydrogen storage and dehydrogenation for hydrogen reconversion. In the exothermic hydrogenation reaction, hydrogen‐lean compounds are converted to hydrogen‐rich compounds, storing hydrogen from various sources such as water electrolysis, fossil fuel reforming, biomass processing, and industrial by‐products. Conversely, hydrogen is extracted from hydrogen‐rich compounds through an endothermic dehydrogenation reaction and supplied to several hydrogenation utilization offtakers. This review article discusses the development trends in catalytic hydrogenation processes for various LOHC materials, including benzene, toluene, naphthalene, biphenyl, diphenylmethane, benzyltoluene, dibenzyltoluene, and N‐ethylcarbazole. It introduces references for catalytic hydrogenation processes utilizing both high‐purity and low‐purity (alternatively, mixed) hydrogen feedstocks, with particular emphasis on low‐purity hydrogen applications. The direct storage of hydrogen with minimal purification, using by‐product hydrogen and mixed hydrogen from hydrocarbon and biomass reforming, is crucial for the economic viability of this hydrogen carrier system.
{"title":"Advances in Catalytic Hydrogenation of Liquid Organic Hydrogen Carriers (LOHCs) Using High‐purity and Low‐purity Hydrogen","authors":"Safira Ramadhani, Quan Nguyen Dao, Yoel Imanuel, Muhammad Ridwan, Hyuntae Sohn, Hyansoo Jeong, Keunsoo Kim, Chang Won Yoon, Kwang Ho Song, Yongmin Kim","doi":"10.1002/cctc.202401278","DOIUrl":"https://doi.org/10.1002/cctc.202401278","url":null,"abstract":"Liquid Organic Hydrogen Carriers (LOHCs) are emerging as a promising solution for global hydrogen logistics. The LOHC process involves two primary chemical reactions: hydrogenation for hydrogen storage and dehydrogenation for hydrogen reconversion. In the exothermic hydrogenation reaction, hydrogen‐lean compounds are converted to hydrogen‐rich compounds, storing hydrogen from various sources such as water electrolysis, fossil fuel reforming, biomass processing, and industrial by‐products. Conversely, hydrogen is extracted from hydrogen‐rich compounds through an endothermic dehydrogenation reaction and supplied to several hydrogenation utilization offtakers. This review article discusses the development trends in catalytic hydrogenation processes for various LOHC materials, including benzene, toluene, naphthalene, biphenyl, diphenylmethane, benzyltoluene, dibenzyltoluene, and N‐ethylcarbazole. It introduces references for catalytic hydrogenation processes utilizing both high‐purity and low‐purity (alternatively, mixed) hydrogen feedstocks, with particular emphasis on low‐purity hydrogen applications. The direct storage of hydrogen with minimal purification, using by‐product hydrogen and mixed hydrogen from hydrocarbon and biomass reforming, is crucial for the economic viability of this hydrogen carrier system.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"9 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yvette Szabó, Sándor Balázs Nagy, Adél Anna Ádám, Rebeka Mészáros, Zoltán Kónya, Ákos Kukovecz, Pál Sipos, Szabados Márton
Herein, we report a base‐catalyzed transesterification reaction of glycerol, a waste product of the biodiesel industry, with various dialkyl carbonates, which act both as reactants and solvents, to convert glycerol carbonate into an industrially useful molecular building block. The catalyst, being used for the first time, is also a waste product from industry, present in bauxite residues and in the Portland cement, simply known as tricalcium aluminate. Despite being well‐known and readily available, this solid is only extremely poorly researched catalyst, nevertheless, using dimethyl and diethyl carbonate, glycerol conversion rates >80% and glycerol carbonate yields >60% could be achieved in just 1 hour (under air atmosphere, and reflux). In a comparison of the performance with other catalysts commonly researched today, as well as with other components of red mud and cements, the results showed that tricalcium aluminate is excellent, cheap and largely environmentally friendly material for this purpose. Reusability studies of the catalysts have also shown that they provide high conversion and product yields even after repeated use, although different material characterization techniques showed intense glycerol‐catalyst surface interaction and intermediate product formation, the deactivating side effects of which could be avoided by catalyst regeneration steps.
{"title":"Valorization of Glycerol to Glycerol Carbonate and Glycidol by Different Dialkyl Carbonates Utilizing Tricalcium Aluminate Hexahydrate as Transesterification Catalyst","authors":"Yvette Szabó, Sándor Balázs Nagy, Adél Anna Ádám, Rebeka Mészáros, Zoltán Kónya, Ákos Kukovecz, Pál Sipos, Szabados Márton","doi":"10.1002/cctc.202401217","DOIUrl":"https://doi.org/10.1002/cctc.202401217","url":null,"abstract":"Herein, we report a base‐catalyzed transesterification reaction of glycerol, a waste product of the biodiesel industry, with various dialkyl carbonates, which act both as reactants and solvents, to convert glycerol carbonate into an industrially useful molecular building block. The catalyst, being used for the first time, is also a waste product from industry, present in bauxite residues and in the Portland cement, simply known as tricalcium aluminate. Despite being well‐known and readily available, this solid is only extremely poorly researched catalyst, nevertheless, using dimethyl and diethyl carbonate, glycerol conversion rates >80% and glycerol carbonate yields >60% could be achieved in just 1 hour (under air atmosphere, and reflux). In a comparison of the performance with other catalysts commonly researched today, as well as with other components of red mud and cements, the results showed that tricalcium aluminate is excellent, cheap and largely environmentally friendly material for this purpose. Reusability studies of the catalysts have also shown that they provide high conversion and product yields even after repeated use, although different material characterization techniques showed intense glycerol‐catalyst surface interaction and intermediate product formation, the deactivating side effects of which could be avoided by catalyst regeneration steps.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"6 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Density functional theory‐based molecular dynamics combined with an explicit solvation model were employed to elucidate the O‐O further bond formation step in Fe‐TAML catalyzed water oxidation reaction. The water nucleophilic attack (WNA) and nitrate nucleophilic attack (NNA) on the oxo group of the high‐valent [TAML+•‐Fe5+=O] species were calculated to have comparable active barriers (24 kcal/mol vs. 22 kcal/mol). This suggests nitrate ion can behave as a co‐catalyst to promote the O‐O bond formation. More importantly, a crucial role of the presence and thermal motion of solvent water in the NNA process was observed. This was quantified by an increase of the activation energy barrier by 4 kcal/mol, determined by comparing the explicit solvent DFT‐MD simulation with implicit solvent static DFT calculation.
基于密度泛函理论的分子动力学结合显式溶解模型阐明了 Fe-TAML 催化水氧化反应中 O-O 进一步成键的步骤。根据计算，水对高价[TAML+--Fe5+=O]物种氧化基团的亲核攻击（WNA）和硝酸根对其的亲核攻击（NNA）具有相似的活性障碍（24 kcal/mol vs. 22 kcal/mol）。这表明硝酸根离子可以作为助催化剂促进 O-O 键的形成。更重要的是，我们观察到溶剂水的存在和热运动在 NNA 过程中起着至关重要的作用。通过比较显式溶剂 DFT-MD 模拟与隐式溶剂静态 DFT 计算得出的活化能势垒增加了 4 kcal/mol，从而量化了这一作用。
{"title":"Unraveling the Role of the Nitrate Ion and Solvent Water on the O‐O Bond Formation Step in Fe‐TAML Catalyzed Water Oxidation","authors":"Rong-Zhen Liao, Ying-Ying Li, Aaron Eisses, Evert Jan Meijer, Si-Xiang Chen","doi":"10.1002/cctc.202401356","DOIUrl":"https://doi.org/10.1002/cctc.202401356","url":null,"abstract":"Density functional theory‐based molecular dynamics combined with an explicit solvation model were employed to elucidate the O‐O further bond formation step in Fe‐TAML catalyzed water oxidation reaction. The water nucleophilic attack (WNA) and nitrate nucleophilic attack (NNA) on the oxo group of the high‐valent [TAML+•‐Fe5+=O] species were calculated to have comparable active barriers (24 kcal/mol vs. 22 kcal/mol). This suggests nitrate ion can behave as a co‐catalyst to promote the O‐O bond formation. More importantly, a crucial role of the presence and thermal motion of solvent water in the NNA process was observed. This was quantified by an increase of the activation energy barrier by 4 kcal/mol, determined by comparing the explicit solvent DFT‐MD simulation with implicit solvent static DFT calculation.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"5 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NH3 is not only an important chemical raw material, but also a high energy storage chemical with zero carbon. Electrocatalytic nitrogen reduction reaction (NRR), which can be driven by clean electric energy under ambient conditions, have become a promising technology for NH3 synthesis due to their environmentally friendly properties. Due to the limitations of low yield and high overpotential, efficient catalysts are urgently needed to solve this problem. In this study, based on density functional theory method and high throughput screening strategy, the NRR was investigated on transition metal single atom anchored to two-dimensional B2C3P surface (TM@B2C3P) as single-atom catalysts (SACs). The results showed that V@B2C3P and Ti@B2C3P have good catalytic properties, and the limiting potentials via the enzymatic pathway were −0.10 and −0.24 V, respectively. Furthermore, the charge density difference and crystal orbital Hamilton population calculations demonstrated that the high catalytic activity can be attributed to the obvious charge transfer between TM@B2C3P and the adsorption intermediates. It is hoped that this work can play a certain role in exploring the application of SACs in NRR.
{"title":"Computational insight into transition metal atoms anchored on B2C3P as single-atom electrocatalysts for nitrogen reduction reaction","authors":"Pengfei Ma, Liwei Jiang, Chengsong Liu, Zhijun Yang, Wei Song, Chaozheng He, Tao Zhang","doi":"10.1002/cctc.202401325","DOIUrl":"https://doi.org/10.1002/cctc.202401325","url":null,"abstract":"NH3 is not only an important chemical raw material, but also a high energy storage chemical with zero carbon. Electrocatalytic nitrogen reduction reaction (NRR), which can be driven by clean electric energy under ambient conditions, have become a promising technology for NH3 synthesis due to their environmentally friendly properties. Due to the limitations of low yield and high overpotential, efficient catalysts are urgently needed to solve this problem. In this study, based on density functional theory method and high throughput screening strategy, the NRR was investigated on transition metal single atom anchored to two-dimensional B2C3P surface (TM@B2C3P) as single-atom catalysts (SACs). The results showed that V@B2C3P and Ti@B2C3P have good catalytic properties, and the limiting potentials via the enzymatic pathway were −0.10 and −0.24 V, respectively. Furthermore, the charge density difference and crystal orbital Hamilton population calculations demonstrated that the high catalytic activity can be attributed to the obvious charge transfer between TM@B2C3P and the adsorption intermediates. It is hoped that this work can play a certain role in exploring the application of SACs in NRR.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"15 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of an efficient catalyst that can selectively activate and generate hydrogen molecules is in urgent demand. Inspired by the 5d rhenium‐tris(thiolate) complex that is capable of catalytically producing and oxidizing H2, the mechanisms of electrocatalytic H2 oxidation (HOR) and evolution (HER) catalyzed by the 4d technetium‐tri(thiolate) analogs, [TcL3] (L = diphenylphosphinobenzenethiolate, a noninnocent ligand), were investigated by DFT calculations, aiming at elucidating the role of the metal in metal‐ligand cooperativity. DFT calculations anticipate high reactivity in both HOR and HER for [TcL3] beyond that of its Re counterparts. Substituting the Re metal for Tc in metal‐tris(thiolate) complexes results in a greater thiyl‐radical character in the Tc complex compared to that in Re. Even when both complexes evolve H2 with similar [ECEC] mechanisms, the proton relays behave with a distinct disparity, featuring the S ligand in the Tc species as compared to the metal‐hydride in Re. The HOR mechanism also bifurcates as [TcL3]2+ is predicted to mainly occur via the ligand‐based pathway, in contrast to the predominant metal and ligand‐based reactivity for Re. This study established the role of the metal in HER and HOR while emphasizing the utility of such metal‐DPPBT cooperativity in the catalytic process.
目前急需开发一种能够选择性激活和生成氢分子的高效催化剂。受能够催化产生和氧化 H2 的 5d 铼-三（硫醇酸盐）复合物的启发，我们通过 DFT 计算研究了 4d 锝-三（硫醇酸盐）类似物 [TcL3]（L = 二苯基膦苯硫酚，一种非无毒配体）催化电催化 H2 氧化（HOR）和进化（HER）的机理，旨在阐明金属在金属-配体合作中的作用。DFT 计算结果表明，[TcL3] 在 HOR 和 HER 中的高反应活性超过了其 Re 配体。在金属-三（硫醇酸盐）配合物中，用 Re 金属代替 Tc 会导致 Tc 配合物中的巯基自由基比 Re 中的更大。即使两种复合物都以类似的[ECEC]机制演化出 H2，质子中继的表现也有明显的差异，Tc 复合物中的 S 配体与 Re 复合物中的金属-酸酐相比更具特色。根据预测，[TcL3]2+ 主要通过配体途径发生，因此 HOR 机制也会发生分叉，这与 Re 中主要的金属和配体反应形成鲜明对比。这项研究确定了金属在 HER 和 HOR 中的作用，同时强调了金属-DPPBT 在催化过程中的协同作用。
{"title":"Comparative Electrocatalysis of Hydrogen Production and Oxidation: Technetium vs Rhenium Tris(thiolate) Complexes","authors":"Xuelian Li, Yingke Wang, Cheng Xu, Zeyi Guo, Yazhu Lu, Deqing Kong, Junfei Wang, Jia Guan, Hao Tang","doi":"10.1002/cctc.202400830","DOIUrl":"https://doi.org/10.1002/cctc.202400830","url":null,"abstract":"The development of an efficient catalyst that can selectively activate and generate hydrogen molecules is in urgent demand. Inspired by the 5d rhenium‐tris(thiolate) complex that is capable of catalytically producing and oxidizing H2, the mechanisms of electrocatalytic H2 oxidation (HOR) and evolution (HER) catalyzed by the 4d technetium‐tri(thiolate) analogs, [TcL3] (L = diphenylphosphinobenzenethiolate, a noninnocent ligand), were investigated by DFT calculations, aiming at elucidating the role of the metal in metal‐ligand cooperativity. DFT calculations anticipate high reactivity in both HOR and HER for [TcL3] beyond that of its Re counterparts. Substituting the Re metal for Tc in metal‐tris(thiolate) complexes results in a greater thiyl‐radical character in the Tc complex compared to that in Re. Even when both complexes evolve H2 with similar [ECEC] mechanisms, the proton relays behave with a distinct disparity, featuring the S ligand in the Tc species as compared to the metal‐hydride in Re. The HOR mechanism also bifurcates as [TcL3]2+ is predicted to mainly occur via the ligand‐based pathway, in contrast to the predominant metal and ligand‐based reactivity for Re. This study established the role of the metal in HER and HOR while emphasizing the utility of such metal‐DPPBT cooperativity in the catalytic process.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"6 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paul Dalby, Weina Li, Weinfeng Shen, Niccolo A. E. Venanzi, Cheng Zhang, Yiwen Li, Daidi Fan
Activity and thermostability are critical yet challenging to improve simultaneously in enzymes. Using directed evolution, we previously identified bovine enterokinase (EKL) variants with enhanced soluble expression and thermal stability. Partial least squares (PLS) analysis of 321 EKL variants revealed the impact of individual mutations and identified neutral or detrimental mutations in top‐performing variants. Leveraging PLS rankings, we created new variants with fewer mutations and enhanced stability. Most original and PLS‐guided variants exhibited an activity‐stability trade‐off. However, two new triple‐ and quadruple‐mutants improved both activity and stability, surpassing the trade‐off limit. Recombining PLS‐guided mutations likely eliminated neutral or harmful mutations, enhancing stability. MD simulations linked residue‐specific dynamics with stability, pinpointing critical structural regions near aggregation‐prone areas. Our findings validate PLS as a potent strategy to enhance enzyme properties, complementing directed evolution.
{"title":"PLS‐guided Mutant Recombination to Improve the Stability of Bovine Enterokinases Obtained by Directed Evolution","authors":"Paul Dalby, Weina Li, Weinfeng Shen, Niccolo A. E. Venanzi, Cheng Zhang, Yiwen Li, Daidi Fan","doi":"10.1002/cctc.202400943","DOIUrl":"https://doi.org/10.1002/cctc.202400943","url":null,"abstract":"Activity and thermostability are critical yet challenging to improve simultaneously in enzymes. Using directed evolution, we previously identified bovine enterokinase (EKL) variants with enhanced soluble expression and thermal stability. Partial least squares (PLS) analysis of 321 EKL variants revealed the impact of individual mutations and identified neutral or detrimental mutations in top‐performing variants. Leveraging PLS rankings, we created new variants with fewer mutations and enhanced stability. Most original and PLS‐guided variants exhibited an activity‐stability trade‐off. However, two new triple‐ and quadruple‐mutants improved both activity and stability, surpassing the trade‐off limit. Recombining PLS‐guided mutations likely eliminated neutral or harmful mutations, enhancing stability. MD simulations linked residue‐specific dynamics with stability, pinpointing critical structural regions near aggregation‐prone areas. Our findings validate PLS as a potent strategy to enhance enzyme properties, complementing directed evolution.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"34 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268806","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Miguel A. Sierra, Sergio Aguado, Albert Gallego-Gamo, Diego J Vicent, Albert Granados, Laura Mallon, Carolina Gimbert-Suriñach, Jordi García-Antón, Luis Casarrubios, Adelina Vallribera
Complexes [(μ‐S₂C₂H₄NHR)Fe₂(CO)₆] (R = p‐C₆H₄‐OCO(CH₂)₉Br (3a); R = p‐C₆H₄‐OCO(CH₂)₈CH₃ (3b)) were used as stabilizing agents in the synthesis of Ni@3 and Au@3 nanoparticles (NPs), which are the first reported stable metallic NPs decorated with [(μ‐S₂C₂H₄NHR)Fe₂(CO)₆] moieties. Electrochemical analysis reveals that incorporating the hydrogenase mimic into the NPs lowers the overpotential and enhances proton reduction electrocatalytic activity in organic media. The NPs act similarly to the [Fe₄S₄] cluster in natural enzymes, functioning as an electron reservoir/relay.
{"title":"Hybrid Nanoparticles: Ni and Au Decorated with [FeFe]‐Hydrogenase Mimics","authors":"Miguel A. Sierra, Sergio Aguado, Albert Gallego-Gamo, Diego J Vicent, Albert Granados, Laura Mallon, Carolina Gimbert-Suriñach, Jordi García-Antón, Luis Casarrubios, Adelina Vallribera","doi":"10.1002/cctc.202401293","DOIUrl":"https://doi.org/10.1002/cctc.202401293","url":null,"abstract":"Complexes [(μ‐S₂C₂H₄NHR)Fe₂(CO)₆] (R = p‐C₆H₄‐OCO(CH₂)₉Br (3a); R = p‐C₆H₄‐OCO(CH₂)₈CH₃ (3b)) were used as stabilizing agents in the synthesis of Ni@3 and Au@3 nanoparticles (NPs), which are the first reported stable metallic NPs decorated with [(μ‐S₂C₂H₄NHR)Fe₂(CO)₆] moieties. Electrochemical analysis reveals that incorporating the hydrogenase mimic into the NPs lowers the overpotential and enhances proton reduction electrocatalytic activity in organic media. The NPs act similarly to the [Fe₄S₄] cluster in natural enzymes, functioning as an electron reservoir/relay.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"23 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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