Optically active amine represents the most important structure motif in natural products and biologically active compounds. Stereoselective reductive addition of imine with the utilization of electrophilic component offers a concise and operationally simple method for the synthesis of chiral amines. This review mainly highlights recent significant synthetic methodology developments in reductive addition of imine for chiral amine synthesis including chiral auxiliary‐mediated diastereoselective transformation, asymmetric transition‐metal catalysis, organocatalysis and enzymatic catalysis. In addition, the electrophilic reagents scopes and mechanistic aspects have also been introduced in this review.
{"title":"Catalytic Reductive Addition of Imine for Chiral Amine Synthesis: Recent Advances and Future Perspectives","authors":"Tingting Xia, Zhiying Yu, Xianqing Wu, Jingping Qu, Yifeng Chen","doi":"10.1002/cctc.202401407","DOIUrl":"https://doi.org/10.1002/cctc.202401407","url":null,"abstract":"Optically active amine represents the most important structure motif in natural products and biologically active compounds. Stereoselective reductive addition of imine with the utilization of electrophilic component offers a concise and operationally simple method for the synthesis of chiral amines. This review mainly highlights recent significant synthetic methodology developments in reductive addition of imine for chiral amine synthesis including chiral auxiliary‐mediated diastereoselective transformation, asymmetric transition‐metal catalysis, organocatalysis and enzymatic catalysis. In addition, the electrophilic reagents scopes and mechanistic aspects have also been introduced in this review.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"93 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253394","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}
Xiaoxue Lin, Xiaoying Peng, Suqin Wu, Chen Ma, Dou Chen, Quanming Peng, Kai Yang, Fan Liu, Shungao Yin, Guiming Peng
The unsatisfied visible light harvesting, slow charge separation, and limited practical surface area of carbon nitride (CN) constrain its performance in photocatalytic water splitting and environmental remediation. Herein, the thermal vapor‐assisted π‐conjugation modification of CN by grafting with p‐aminophenoxy groups was developed to tune the photophysical properties of CN to enhance its photocatalytic activity. Besides extending the light absorption, the surface modification constructed a nanojunction across the depth direction, which leads to facilitated charge separation and transfer. In addition, the thermal vapor modification process thermally etches and trims the pristine CN to be highly holey structure, resulting to >10 times increase in specific surface area. Photocatalysis results showed that the obtained modified CN yielded hydrogen from photocatalytic water splitting at a rate of 7.82 mmol/g/h, over 7‐folds as that of pristine CN, with quantum yield of 3.28% at 400 nm. The π‐conjugation modified CN also demonstrated enhanced photocatalytic environmental remediation application, exemplified by much faster photodegradation of tetracycline hydrochloride. This work provides the thermal vapor surface chemical modification of CN as a promising integrated pathway of multiple favorable photophysical properties towards efficient photocatalysis application.
{"title":"Surface Nanojunction Enabled by Vapor‐Assisted π‐Conjugation Modification of Carbon Nitride for Enhanced Photocatalytic Water Splitting","authors":"Xiaoxue Lin, Xiaoying Peng, Suqin Wu, Chen Ma, Dou Chen, Quanming Peng, Kai Yang, Fan Liu, Shungao Yin, Guiming Peng","doi":"10.1002/cctc.202401408","DOIUrl":"https://doi.org/10.1002/cctc.202401408","url":null,"abstract":"The unsatisfied visible light harvesting, slow charge separation, and limited practical surface area of carbon nitride (CN) constrain its performance in photocatalytic water splitting and environmental remediation. Herein, the thermal vapor‐assisted π‐conjugation modification of CN by grafting with p‐aminophenoxy groups was developed to tune the photophysical properties of CN to enhance its photocatalytic activity. Besides extending the light absorption, the surface modification constructed a nanojunction across the depth direction, which leads to facilitated charge separation and transfer. In addition, the thermal vapor modification process thermally etches and trims the pristine CN to be highly holey structure, resulting to >10 times increase in specific surface area. Photocatalysis results showed that the obtained modified CN yielded hydrogen from photocatalytic water splitting at a rate of 7.82 mmol/g/h, over 7‐folds as that of pristine CN, with quantum yield of 3.28% at 400 nm. The π‐conjugation modified CN also demonstrated enhanced photocatalytic environmental remediation application, exemplified by much faster photodegradation of tetracycline hydrochloride. This work provides the thermal vapor surface chemical modification of CN as a promising integrated pathway of multiple favorable photophysical properties towards efficient photocatalysis application.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"9 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253437","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}
Regine Siedentop, Maximilian Siska, Johanna Hermes, Stephan Lütz, Eric von Lieres, Katrin Rosenthal
The optimization of enzyme cascades is a complex and resource-demanding task due to the multitude of parameters and synergistic effects involved. Machine learning can support the identification of optimal reaction conditions, for example, in the case of Bayesian optimization (BO), by proposing new experiments based on Gaussian process regression (GPR) and expected improvement (EI). Here, we used BO to optimize the concentrations of the reaction components of an enzyme cascade. The productivity-cost-ratio was chosen as the optimization objective in order to achieve the highest possible productivity, which was normalized to the costs of the materials used to prevent convergence to ever-increasing enzyme concentrations. To reduce the experimental effort, contrary to common practice in biological experiments, we did not use replicates but instead relied on the algorithm’s proposed experiments and inherent uncertainty quantification. This approach balances parameter space exploration and exploitation, which is critical for the efficient and effective identification of optimal reaction conditions. At the optimized reaction conditions identified in our study, the productivity-cost ratio was doubled to 38.6 mmol L-1 h-1 €-1 compared to a reference experiment. The parameter optimization required only 52 experiments while being robust to outlying experimental results.
{"title":"Avoiding Replicates in Biocatalysis Experiments: Machine Learning for Enzyme Cascade Optimization","authors":"Regine Siedentop, Maximilian Siska, Johanna Hermes, Stephan Lütz, Eric von Lieres, Katrin Rosenthal","doi":"10.1002/cctc.202400777","DOIUrl":"https://doi.org/10.1002/cctc.202400777","url":null,"abstract":"The optimization of enzyme cascades is a complex and resource-demanding task due to the multitude of parameters and synergistic effects involved. Machine learning can support the identification of optimal reaction conditions, for example, in the case of Bayesian optimization (BO), by proposing new experiments based on Gaussian process regression (GPR) and expected improvement (EI). Here, we used BO to optimize the concentrations of the reaction components of an enzyme cascade. The productivity-cost-ratio was chosen as the optimization objective in order to achieve the highest possible productivity, which was normalized to the costs of the materials used to prevent convergence to ever-increasing enzyme concentrations. To reduce the experimental effort, contrary to common practice in biological experiments, we did not use replicates but instead relied on the algorithm’s proposed experiments and inherent uncertainty quantification. This approach balances parameter space exploration and exploitation, which is critical for the efficient and effective identification of optimal reaction conditions. At the optimized reaction conditions identified in our study, the productivity-cost ratio was doubled to 38.6 mmol L-1 h-1 €-1 compared to a reference experiment. The parameter optimization required only 52 experiments while being robust to outlying experimental results.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"12 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253386","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 conversion of methane to methanol (MTM) represents a pivotal objective in the C1 chemical industry. Transition metal, such as iron, exchanged zeolites are one category of the most active catalysts for direct conversion of MTM. One important topic in understanding the mechanism of Fe-zeolite catalyzed MTM is how the heterogeneity of catalytic (Fe) sites influences the system stability and reactivity. Employing DFT calculations and machine learning method, we herein studied the stability-reactivity relationship of a MTM catalytic cycle with N2O as the oxidant over Fe-exchanged zeolites. The Fe heterogeneity was introduced by using CHA and FER zeolites and looking at a number of related Fe species (FeII, FeO, and FeOH). A strong correlation was observed between the stability of such Fe species, which is primarily determined by the formation energy of FeII, and such a stability trend remains consistent throughout the MTM catalytic cycle. The reactivity analysis then demonstrated that less stable Fe species can exhibit higher reactivity when situated in specific sites. Further machine learning analysis validated the significant relevance of activation barriers with reaction energies in N2O decomposition step that is not sufficiently captured by the traditional one-dimensional Brønsted–Evans–Polanyi (BEP) relationship.
{"title":"On the Heterogeneity of Iron-Oxo Species in Zeolites for the Oxidation of Methane to Methanol by Nitrous Oxide: A Theoretical Perspective","authors":"Shuo Wang, Chenchen Li, Chong Liu, Wei Zhuang","doi":"10.1002/cctc.202401416","DOIUrl":"https://doi.org/10.1002/cctc.202401416","url":null,"abstract":"The conversion of methane to methanol (MTM) represents a pivotal objective in the C1 chemical industry. Transition metal, such as iron, exchanged zeolites are one category of the most active catalysts for direct conversion of MTM. One important topic in understanding the mechanism of Fe-zeolite catalyzed MTM is how the heterogeneity of catalytic (Fe) sites influences the system stability and reactivity. Employing DFT calculations and machine learning method, we herein studied the stability-reactivity relationship of a MTM catalytic cycle with N2O as the oxidant over Fe-exchanged zeolites. The Fe heterogeneity was introduced by using CHA and FER zeolites and looking at a number of related Fe species (FeII, FeO, and FeOH). A strong correlation was observed between the stability of such Fe species, which is primarily determined by the formation energy of FeII, and such a stability trend remains consistent throughout the MTM catalytic cycle. The reactivity analysis then demonstrated that less stable Fe species can exhibit higher reactivity when situated in specific sites. Further machine learning analysis validated the significant relevance of activation barriers with reaction energies in N2O decomposition step that is not sufficiently captured by the traditional one-dimensional Brønsted–Evans–Polanyi (BEP) relationship.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"66 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253387","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}
Biomass-based saccharide valorization to produce lactic acid (LaA) via chemocatalysis has emerged as a promising approach to meet the substantial demand of global LaA market, whereas the manufacture of prominent heterogeneous catalyst is still challenging. Herein, we fabricate a series of heterogeneous rare earth catalysts, and indicate that Er supported onto titanium silicate-1 (TS-1) exhibits better activity than other rare earth catalysts for glucose transformation towards LaA. Remarkably, coupling Sn with Er onto TS-1 enabled the sharp increment of LaA yield, and 3Sn15Er/TS-1 catalyst outperformed other heterogeneous rare earth catalysts as reported to date, giving as high as 82.2 % and 76.2% yields of LaA from sorbose and glucose, respectively. The catalyst characterization demonstrated the coexistence of Er2O3 and Sn2Er2O7 on 3Sn15Er/TS-1 catalyst, both of which contributed to LaA production. Sn doping favored the formation of active particles in smaller size and increased the Lewis acidic sites when compared to single 15Er/TS-1, thereby promoting the isomerization and retro-aldol reaction of glucose to C3 intermediates. 3Sn15Er/TS-1 catalyst also showed universal activity for diverse biomass-based saccharides. This work might give useful insights to explore heterogeneous rare earth catalysts with superior activity in biomass valorization.
以生物质为基础，通过化学催化将糖转化为乳酸（LaA），已成为满足全球 LaA 市场巨大需求的一种前景广阔的方法，但制造杰出的异相催化剂仍具有挑战性。在本文中，我们制备了一系列异相稀土催化剂，结果表明，在葡萄糖转化为 LaA 的过程中，硅酸钛-1（TS-1）支撑的 Er 比其他稀土催化剂表现出更好的活性。值得注意的是，将 Sn 与 Er 耦合到 TS-1 上可使 LaA 产率大幅提高，3Sn15Er/TS-1 催化剂的性能优于迄今报道的其他异质稀土催化剂，从山梨糖和葡萄糖制得的 LaA 产率分别高达 82.2% 和 76.2%。催化剂表征结果表明，3Sn15Er/TS-1 催化剂上共存有 Er2O3 和 Sn2Er2O7，它们都有助于 LaA 的生成。与单一的 15Er/TS-1 相比，掺杂 Sn 有利于形成更小尺寸的活性颗粒，并增加了路易斯酸位点，从而促进了葡萄糖向 C3 中间体的异构化和逆醛化反应。3Sn15Er/TS-1 催化剂还显示出对多种生物质糖类的普遍活性。这项工作可能会为探索在生物质资源化方面具有卓越活性的异质稀土催化剂提供有益的启示。
{"title":"Titanium Silicate-1 Coupled with Sn and Er as Effective Catalysts for the Production of Lactic Acid from Saccharides","authors":"Wenyu Zhang, Jingying Qin, Shengqi Liao, Guiying Li, Jianmei Li, Changwei Hu","doi":"10.1002/cctc.202401303","DOIUrl":"https://doi.org/10.1002/cctc.202401303","url":null,"abstract":"Biomass-based saccharide valorization to produce lactic acid (LaA) via chemocatalysis has emerged as a promising approach to meet the substantial demand of global LaA market, whereas the manufacture of prominent heterogeneous catalyst is still challenging. Herein, we fabricate a series of heterogeneous rare earth catalysts, and indicate that Er supported onto titanium silicate-1 (TS-1) exhibits better activity than other rare earth catalysts for glucose transformation towards LaA. Remarkably, coupling Sn with Er onto TS-1 enabled the sharp increment of LaA yield, and 3Sn15Er/TS-1 catalyst outperformed other heterogeneous rare earth catalysts as reported to date, giving as high as 82.2 % and 76.2% yields of LaA from sorbose and glucose, respectively. The catalyst characterization demonstrated the coexistence of Er2O3 and Sn2Er2O7 on 3Sn15Er/TS-1 catalyst, both of which contributed to LaA production. Sn doping favored the formation of active particles in smaller size and increased the Lewis acidic sites when compared to single 15Er/TS-1, thereby promoting the isomerization and retro-aldol reaction of glucose to C3 intermediates. 3Sn15Er/TS-1 catalyst also showed universal activity for diverse biomass-based saccharides. This work might give useful insights to explore heterogeneous rare earth catalysts with superior activity in biomass valorization.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"15 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253388","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}
Urea (CO(NH2)2) is the main component of nitrogen-based fertilizers and is widely used in various industries. Until now, urea production is conducted under high-temperature and high-pressure conditions, which involves a considerable carbon footprint. Urea electrosynthesis, which is powered by renewable-energy-derived electricity, has emerged as a sustainable single-step process for urea production. The development of efficient and stable catalysts is the key to improving the efficiency of urea electrosynthesis. In this review, we summarized the research progress and applications of catalysts with atomic-scale reactive sites in urea electrosynthesis. Firstly, the catalytic mechanisms of urea electrosynthesis from CO2 and various nitrogenous molecules are discussed. Then, typical electrocatalysts such as single atom electrocatalysts, dual atom electrocatalysts, clusters, atomic dopants, and vacancies, etc., are discussed. Furthermore, characterization methods for atomic-scale reactive sites are summarized. Finally, challenges and suggestions for urea electrosynthesis are proposed. We hope this review can provide some inspiration toward the development of catalysts for efficient and sustainable urea electrosynthesis.
{"title":"Research Progress of Catalysts with Atomic-Scale Reactive Sites in Urea Electrosynthesis","authors":"Lu Lu, Peng Zhan, Xuehan Chen, Wei Shi, Zhihao Si, Peiyong Qin","doi":"10.1002/cctc.202401130","DOIUrl":"https://doi.org/10.1002/cctc.202401130","url":null,"abstract":"Urea (CO(NH2)2) is the main component of nitrogen-based fertilizers and is widely used in various industries. Until now, urea production is conducted under high-temperature and high-pressure conditions, which involves a considerable carbon footprint. Urea electrosynthesis, which is powered by renewable-energy-derived electricity, has emerged as a sustainable single-step process for urea production. The development of efficient and stable catalysts is the key to improving the efficiency of urea electrosynthesis. In this review, we summarized the research progress and applications of catalysts with atomic-scale reactive sites in urea electrosynthesis. Firstly, the catalytic mechanisms of urea electrosynthesis from CO2 and various nitrogenous molecules are discussed. Then, typical electrocatalysts such as single atom electrocatalysts, dual atom electrocatalysts, clusters, atomic dopants, and vacancies, etc., are discussed. Furthermore, characterization methods for atomic-scale reactive sites are summarized. Finally, challenges and suggestions for urea electrosynthesis are proposed. We hope this review can provide some inspiration toward the development of catalysts for efficient and sustainable urea electrosynthesis.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"2 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253390","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 distinctive interplay between abundant transition metal-containing active sites and their surrounding outer coordination sphere (OCS) is pivotal in achieving remarkable catalytic responses. In this context, copper complexes continue to garner attention as promising catalysts for the Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER). In this article, we report two macrocyclic binuclear Cu complexes having variable peripheral functionalities around a common N2O2 like core. A mononuclear complex bearing the salophen-type ligand design was used as a control. The complex featuring peripheral OH groups, demonstrates highest catalytic activity in ORR (3050 s-1) and OER (6700 s-1), suggesting the crucial role of the alcoholic group during catalysis. In contrast, the mononuclear complex necessitates an additional thermodynamic stimulus to attain catalytic conditions for ORR and OER obverse to the case of binuclear complexes. Hence, this study establishes a template for designing molecular catalysts to mediate energy-relevant multielectron/multiproton reactions in both oxidizing and reducing environments.
{"title":"Bimetallic Copper Complexes for Electrocatalytic Bidirectional O2/H2O Conversion in Aqueous Solution","authors":"Afsar Ali, Divyansh Prakash, Abhishek Saini, Chandan Das, Naseer Ahmed Shah, Arnab Dutta","doi":"10.1002/cctc.202401228","DOIUrl":"https://doi.org/10.1002/cctc.202401228","url":null,"abstract":"The distinctive interplay between abundant transition metal-containing active sites and their surrounding outer coordination sphere (OCS) is pivotal in achieving remarkable catalytic responses. In this context, copper complexes continue to garner attention as promising catalysts for the Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER). In this article, we report two macrocyclic binuclear Cu complexes having variable peripheral functionalities around a common N2O2 like core. A mononuclear complex bearing the salophen-type ligand design was used as a control. The complex featuring peripheral OH groups, demonstrates highest catalytic activity in ORR (3050 s-1) and OER (6700 s-1), suggesting the crucial role of the alcoholic group during catalysis. In contrast, the mononuclear complex necessitates an additional thermodynamic stimulus to attain catalytic conditions for ORR and OER obverse to the case of binuclear complexes. Hence, this study establishes a template for designing molecular catalysts to mediate energy-relevant multielectron/multiproton reactions in both oxidizing and reducing environments.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"19 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253391","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}
Armel F.T. Waffo, Meritxell Wu Lu, Sagie Katz, Stefan Frielingsdorf, Benjamin R Duffus, Jan Liedtke, Silke Leimkühler, Oliver Lenz, Konstantin Laun, Maria Andrea Mroginski, Ingo Zebger
Sophisticated enzymatic systems have evolved in nature to efficiently couple distinct biochemical reactions in form of cascades. As such they serve as reference models to understand the indirect interactions of catalytic centers. Herein, we studied, in solution, the coupling of the reactions from membrane‐bound [NiFe] hydrogenase (MBH) from Cupriavidus necator (reversible H2 splitting into H+ and e‐) and the molybdenum‐dependent formate dehydrogenase from Rhodobacter capsulatus (reversible formate to CO2 interconversion). To follow their interplay via the characteristic absorptions from the MBH's active site or the respective substrate and product bands of FDH, we utilized in situ IR spectrocopy and GC(‐MS), in the absence or presence of soluble redox mediators. Coarse grained molecular dynamics (cgMD) computations revealed the lack of productive enzyme complexes for direct electron transfer (ET). Thus, the observed minor amounts of H2 or formate were produced from transient interactions between the two enzymes. On the contrary, the significantly increased product formation in the presence of methylene viologen can be related to the putative multiple interaction sites of the redox mediator with FDH identified by cgMD. Our study represents a proof‐of‐concept approach that can be used in future to develop novel coupled biocatalytic systems by identifying potential ET pathways.
{"title":"Coupling of the catalytic reactions from formate dehydrogenase and hydrogenase in solution: Insights from computations and in situ IR spectroscopy","authors":"Armel F.T. Waffo, Meritxell Wu Lu, Sagie Katz, Stefan Frielingsdorf, Benjamin R Duffus, Jan Liedtke, Silke Leimkühler, Oliver Lenz, Konstantin Laun, Maria Andrea Mroginski, Ingo Zebger","doi":"10.1002/cctc.202400794","DOIUrl":"https://doi.org/10.1002/cctc.202400794","url":null,"abstract":"Sophisticated enzymatic systems have evolved in nature to efficiently couple distinct biochemical reactions in form of cascades. As such they serve as reference models to understand the indirect interactions of catalytic centers. Herein, we studied, in solution, the coupling of the reactions from membrane‐bound [NiFe] hydrogenase (MBH) from Cupriavidus necator (reversible H2 splitting into H+ and e‐) and the molybdenum‐dependent formate dehydrogenase from Rhodobacter capsulatus (reversible formate to CO2 interconversion). To follow their interplay via the characteristic absorptions from the MBH's active site or the respective substrate and product bands of FDH, we utilized in situ IR spectrocopy and GC(‐MS), in the absence or presence of soluble redox mediators. Coarse grained molecular dynamics (cgMD) computations revealed the lack of productive enzyme complexes for direct electron transfer (ET). Thus, the observed minor amounts of H2 or formate were produced from transient interactions between the two enzymes. On the contrary, the significantly increased product formation in the presence of methylene viologen can be related to the putative multiple interaction sites of the redox mediator with FDH identified by cgMD. Our study represents a proof‐of‐concept approach that can be used in future to develop novel coupled biocatalytic systems by identifying potential ET pathways.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"100 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253395","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}
Yuan Xin, Jieyu Ma, Qian Zhang, Zhizhou Wang, Li Jiang, Haidong Bian, Qianli Zhang, Jie Liu
The electrochemical process of methanol oxidation reaction (MOR), which is closely associated with electrochemical production of formate and hydrogen, is considered a highly viable avenue for advancing renewable energy technologies. Nevertheless, the development and creation of affordable, effective, and durable electrocatalysts for MOR continue to present significant obstacles. In this study, a hierarchical porous NiO/NiCo2O4/NF electrode is fabricated through the integration of solvothermal and thermal oxidation treatments of Ni‐MOF‐74 and NiCo‐Asp. After thoroughly assessing the electrochemical performance for MOR, NiO/NiCo2O4/NF demonstrates a significant current density of 140 mA·cm‐2 at 1.6 V (vs. RHE) and a Tafel slop of 45.0 mV·dec‐1 in 1 M KOH and 0.5 M methanol. The excellent performance of MOR can be ascribed to the hierarchical porous nature that enhances mass and electron transport while offering numerous active sites for electrocatalytic reactions. Additionally, the heterointerface between NiO and NiCo2O4 could further enhance electron transfer rate and reaction kinetics for the MOR. The developed NiO/NiCo2O4/NF electrode shows potential as a viable and economical alternative to Pt‐based electrocatalysts for MOR‐based applications.
甲醇氧化反应（MOR）的电化学过程与甲酸盐和氢气的电化学生产密切相关，被认为是推进可再生能源技术的一个非常可行的途径。然而，开发和创造经济、有效和耐用的甲醇氧化反应电催化剂仍然面临着重大障碍。在本研究中，通过对 Ni-MOF-74 和 NiCo-Asp 进行溶解热处理和热氧化处理，制备出了分层多孔 NiO/NiCo2O4/NF 电极。在全面评估了 MOR 的电化学性能后，NiO/NiCo2O4/NF 在 1.6 V（相对于 RHE）电压下的电流密度达到了 140 mA-cm-2，在 1 M KOH 和 0.5 M 甲醇中的 Tafel slop 值为 45.0 mV-dec-1。MOR 的优异性能可归因于其分层多孔性质，这种性质可增强质量和电子传输，同时为电催化反应提供大量活性位点。此外，NiO 和 NiCo2O4 之间的异质界面可进一步提高 MOR 的电子传输速率和反应动力学。在基于 MOR 的应用中，所开发的 NiO/NiCo2O4/NF 电极具有替代铂基电催化剂的经济可行性。
{"title":"Metal organic frameworks‐derived NiO/NiCo2O4 heterostructures for effective methanol oxidation reaction","authors":"Yuan Xin, Jieyu Ma, Qian Zhang, Zhizhou Wang, Li Jiang, Haidong Bian, Qianli Zhang, Jie Liu","doi":"10.1002/cctc.202401277","DOIUrl":"https://doi.org/10.1002/cctc.202401277","url":null,"abstract":"The electrochemical process of methanol oxidation reaction (MOR), which is closely associated with electrochemical production of formate and hydrogen, is considered a highly viable avenue for advancing renewable energy technologies. Nevertheless, the development and creation of affordable, effective, and durable electrocatalysts for MOR continue to present significant obstacles. In this study, a hierarchical porous NiO/NiCo2O4/NF electrode is fabricated through the integration of solvothermal and thermal oxidation treatments of Ni‐MOF‐74 and NiCo‐Asp. After thoroughly assessing the electrochemical performance for MOR, NiO/NiCo2O4/NF demonstrates a significant current density of 140 mA·cm‐2 at 1.6 V (vs. RHE) and a Tafel slop of 45.0 mV·dec‐1 in 1 M KOH and 0.5 M methanol. The excellent performance of MOR can be ascribed to the hierarchical porous nature that enhances mass and electron transport while offering numerous active sites for electrocatalytic reactions. Additionally, the heterointerface between NiO and NiCo2O4 could further enhance electron transfer rate and reaction kinetics for the MOR. The developed NiO/NiCo2O4/NF electrode shows potential as a viable and economical alternative to Pt‐based electrocatalysts for MOR‐based applications.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"66 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253502","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}
Tie-Qi Xu, Run-Hua Dong, Jia-Yin Guo, Hang-Ming Sun
The development of modern society is closely related to polymer materials. As a typical example, plastic is an indispensable material in modern society. However, despite their low cost and widespread use, most discarded polymers are not recyclable, and their widespread use leads to the depletion of natural resources. In addition, the accumulation of polymer materials and their evolution in the environment can also cause serious environmental problems. Although the polymers can be reused by physical recovery, the properties of the polymers produced by this process are significantly reduced. Chemical recycling to original monomers for repolymerization offers a promising closed‐loop method to transition from linear plastic economy toward a more sustainable circular model. This review focus on recent development and outlines future challenged of emerging chemically recyclable polyesters.
{"title":"Circular Polyesters Based on Lactones","authors":"Tie-Qi Xu, Run-Hua Dong, Jia-Yin Guo, Hang-Ming Sun","doi":"10.1002/cctc.202401319","DOIUrl":"https://doi.org/10.1002/cctc.202401319","url":null,"abstract":"The development of modern society is closely related to polymer materials. As a typical example, plastic is an indispensable material in modern society. However, despite their low cost and widespread use, most discarded polymers are not recyclable, and their widespread use leads to the depletion of natural resources. In addition, the accumulation of polymer materials and their evolution in the environment can also cause serious environmental problems. Although the polymers can be reused by physical recovery, the properties of the polymers produced by this process are significantly reduced. Chemical recycling to original monomers for repolymerization offers a promising closed‐loop method to transition from linear plastic economy toward a more sustainable circular model. This review focus on recent development and outlines future challenged of emerging chemically recyclable polyesters.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"9 1","pages":""},"PeriodicalIF":4.5,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142253396","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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