Prof. Nao Tsunoji, Misae Onishi, Sou Sonoda, Dr. Takeshi Ohnishi, Prof. Masaru Ogura, Prof. Zen Maeno, Prof. Takashi Toyao, Prof. Ken-ichi Shimizu
The Front Cover represents the three formation routes of zeolite from different starting materials. Zeolites are crucial industrial catalysts, whereas their crystallization mechanism is still unclear, limiting their rational functional design. Nao Tsunoji and co-workers present the synthesis–structure–catalysis relation of CHA zeolite to get fundamental knowledge for intentionally controlling the function of zeolites. Different starting materials provide three different formation pathways to form CHA zeolites with different properties in the presence of tetraethylammonium hydroxide as an inexpensive organic structure directing agent. The knowledge related to origin of the catalytic durability was obtained based on their structural character, crystallization mechanism, and exhaust gas purification ability. More information can be found in the Research Article by Nao Tsunoji and co-workers (DOI: 10.1002/cctc.202400459).
封面展示了不同起始材料形成沸石的三种途径。沸石是重要的工业催化剂，但其结晶机理尚不清楚，限制了其合理的功能设计。Nao Tsunoji 及其合作者介绍了 CHA 沸石的合成-结构-催化关系，为有意控制沸石的功能提供了基础知识。不同的起始材料提供了三种不同的形成途径，在作为廉价有机结构引导剂的四乙基氢氧化铵存在下，形成了具有不同性质的 CHA 沸石。根据它们的结构特征、结晶机理和废气净化能力，获得了与催化耐久性起源有关的知识。更多信息，请参阅 Nao Tsunoji 及其合作者的研究文章（DOI: 10.1002/cctc.202400459）。
{"title":"Front Cover: Synthesis-Structure-Catalysis Relations in CHA Zeolites Applied for Selective Catalytic Reduction of NOx with Ammonia (ChemCatChem 16/2024)","authors":"Prof. Nao Tsunoji, Misae Onishi, Sou Sonoda, Dr. Takeshi Ohnishi, Prof. Masaru Ogura, Prof. Zen Maeno, Prof. Takashi Toyao, Prof. Ken-ichi Shimizu","doi":"10.1002/cctc.202481601","DOIUrl":"https://doi.org/10.1002/cctc.202481601","url":null,"abstract":"<p><b>The Front Cover</b> represents the three formation routes of zeolite from different starting materials. Zeolites are crucial industrial catalysts, whereas their crystallization mechanism is still unclear, limiting their rational functional design. Nao Tsunoji and co-workers present the synthesis–structure–catalysis relation of CHA zeolite to get fundamental knowledge for intentionally controlling the function of zeolites. Different starting materials provide three different formation pathways to form CHA zeolites with different properties in the presence of tetraethylammonium hydroxide as an inexpensive organic structure directing agent. The knowledge related to origin of the catalytic durability was obtained based on their structural character, crystallization mechanism, and exhaust gas purification ability. More information can be found in the Research Article by Nao Tsunoji and co-workers (DOI: 10.1002/cctc.202400459).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202481601","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084581","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}
Dr. Mengjiao Wang, Prof. Silvio Osella, Dr. Bruno Torre, Matteo Crisci, Fabian Schmitz, Roberto Altieri, Prof. Enzo Di Fabrizio, Dr. Heinz Amenitsch, Dr. Barbara Sartori, Zheming Liu, Prof. Teresa Gatti, Dr. Francesco Lamberti
2D MoS2/BiOBr van der Waals heterojunctions can be used for photoelectrocatalytic hydrogen production. The Cover Feature shows a MoS2/BiOBr heterojunction working as a photocathode. The photogenerated electrons from BiOBr mainly flow into two directions: one is migrating towards the MoS2 surface, driving the hydrogen evolution reaction; the other is accumulating on BiOBr and reduces BiOBr to metallic Bi. However, in a heterojunction with small ratio of MoS2, the electrons are prone to transfer to MoS2, thus decreasing the accumulation of electrons on BiOBr and preventing it from deactivation. More information can be found in the Research Article by Mengjiao Wang, Francesco Lamberti, and co-workers (DOI: 10.1002/cctc.202400282).
{"title":"Cover Feature: Stabilizing Layered BiOBr Photoelectrocatalyst by Van Der Waals Heterojunction Strategy (ChemCatChem 16/2024)","authors":"Dr. Mengjiao Wang, Prof. Silvio Osella, Dr. Bruno Torre, Matteo Crisci, Fabian Schmitz, Roberto Altieri, Prof. Enzo Di Fabrizio, Dr. Heinz Amenitsch, Dr. Barbara Sartori, Zheming Liu, Prof. Teresa Gatti, Dr. Francesco Lamberti","doi":"10.1002/cctc.202481602","DOIUrl":"https://doi.org/10.1002/cctc.202481602","url":null,"abstract":"<p>2D MoS<sub>2</sub>/BiOBr van der Waals heterojunctions can be used for photoelectrocatalytic hydrogen production. <b>The Cover Feature</b> shows a MoS<sub>2</sub>/BiOBr heterojunction working as a photocathode. The photogenerated electrons from BiOBr mainly flow into two directions: one is migrating towards the MoS<sub>2</sub> surface, driving the hydrogen evolution reaction; the other is accumulating on BiOBr and reduces BiOBr to metallic Bi. However, in a heterojunction with small ratio of MoS<sub>2</sub>, the electrons are prone to transfer to MoS<sub>2</sub>, thus decreasing the accumulation of electrons on BiOBr and preventing it from deactivation. More information can be found in the Research Article by Mengjiao Wang, Francesco Lamberti, and co-workers (DOI: 10.1002/cctc.202400282).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202481602","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084582","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}
Heloise Ribeiro de Barros, Maíra Theisen, Maria Clara Durigon, Daiani C. Leite, Leandro Piovan, Izabel C. Riegel-Vidotti
Temperature-responsive biocatalytic hybrid materials offer several advantages, such as improved stability, enhanced catalytic efficiency, and biocatalysts longer lifespan. Combining enzymes with thermoresponsive polymers in a strategically manner allows a smarter modulation of enzyme activity in response to temperature changes. Thermoresponsive materials can act as protective barriers for enzymes or enable controlled exposure and release depending on temperature variations, expanding enzyme applications in diverse environments. This review aims to comprehensively present the design strategies for enzyme-polymer hybrid materials with thermoresponsive properties, and to address the advantages, applications, and challenges involved for a rational control of biocatalytic systems. The study emphasizes the importance of creating stimuli-responsive biocatalytic hybrid materials for diverse applications, ranging from controlled drug delivery to industrial catalysis. Furthermore, we outline key research opportunities and future perspectives for studies within this scope.
{"title":"Smart Materials for Biocatalysis Regulation through Thermoresponsive Polymers","authors":"Heloise Ribeiro de Barros, Maíra Theisen, Maria Clara Durigon, Daiani C. Leite, Leandro Piovan, Izabel C. Riegel-Vidotti","doi":"10.1002/cctc.202400699","DOIUrl":"https://doi.org/10.1002/cctc.202400699","url":null,"abstract":"Temperature-responsive biocatalytic hybrid materials offer several advantages, such as improved stability, enhanced catalytic efficiency, and biocatalysts longer lifespan. Combining enzymes with thermoresponsive polymers in a strategically manner allows a smarter modulation of enzyme activity in response to temperature changes. Thermoresponsive materials can act as protective barriers for enzymes or enable controlled exposure and release depending on temperature variations, expanding enzyme applications in diverse environments. This review aims to comprehensively present the design strategies for enzyme-polymer hybrid materials with thermoresponsive properties, and to address the advantages, applications, and challenges involved for a rational control of biocatalytic systems. The study emphasizes the importance of creating stimuli-responsive biocatalytic hybrid materials for diverse applications, ranging from controlled drug delivery to industrial catalysis. Furthermore, we outline key research opportunities and future perspectives for studies within this scope.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141945554","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}
Xiaoqiao Zhang, Jian Zheng, Florian Johannes Boch, Simon Nickl, Klaus Köhler
Ruthenium has been supported on specifically chosen non‐reducible supports (Al2O3, SiO2, Al2O3‐SiO2 mixed oxides, Mg/ZnAl2O4 spinel, and AlF3), and these catalysts have been tested in the decomposition of nitrous oxide, N2O, to identify the catalytically active phase of ruthenium. Pure, bulk ruthenium dioxide, RuO2, and isolated Ru surface complexes have been synthesized and investigated for comparison. The catalysts were characterized by X‐ray diffraction, H2 chemisorption, N2 physisorption, temperature‐programmed reduction, and desorption TPR/TPD), andin situ infrared spectroscopy (IR). All aimed experiments strongly indicate that the decomposition of N2O occurs on ruthenium dioxide, RuO2, instead of metal particles. H2 pre‐reduction to Ru metal has inhibitory effects for all oxygen‐containing supports. The activity increases with the dispersion of ruthenium oxide. Bulk RuO2 showed the best catalytic performance.
{"title":"Decomposition of N2O by Ruthenium Catalysts – RuO2 as Active Phase on Non‐Reducible Supports","authors":"Xiaoqiao Zhang, Jian Zheng, Florian Johannes Boch, Simon Nickl, Klaus Köhler","doi":"10.1002/cctc.202400347","DOIUrl":"https://doi.org/10.1002/cctc.202400347","url":null,"abstract":"Ruthenium has been supported on specifically chosen non‐reducible supports (Al2O3, SiO2, Al2O3‐SiO2 mixed oxides, Mg/ZnAl2O4 spinel, and AlF3), and these catalysts have been tested in the decomposition of nitrous oxide, N2O, to identify the catalytically active phase of ruthenium. Pure, bulk ruthenium dioxide, RuO2, and isolated Ru surface complexes have been synthesized and investigated for comparison. The catalysts were characterized by X‐ray diffraction, H2 chemisorption, N2 physisorption, temperature‐programmed reduction, and desorption TPR/TPD), andin situ infrared spectroscopy (IR). All aimed experiments strongly indicate that the decomposition of N2O occurs on ruthenium dioxide, RuO2, instead of metal particles. H2 pre‐reduction to Ru metal has inhibitory effects for all oxygen‐containing supports. The activity increases with the dispersion of ruthenium oxide. Bulk RuO2 showed the best catalytic performance.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141945557","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}
Alkaline water splitting has shown great potential for industrial‐scale hydrogen production. However, its wide application is still limited by the performance of hydrogen evolution reaction (HER) electrocatalysts, which are difficult to achieve ideal current density under low overpotential. Applying the hydrogen spillover effect to enhance HER performance has become an emerging research direction. Although previous studies mainly focused on hydrogen overflow in acidic media, the latest studies have shown that hydrogen overflow also exists under alkaline conditions, and its role in improving HER performance cannot be ignored. In this paper, the characteristic differences of the hydrogen overflow effect under acidic and alkaline conditions were investigated in depth, and the unique behavior of hydrogen overflow in the two different environments and its influence on the catalytic process were analyzed. System hydrogen spillover characterization methods are summarized at the same time, these technologies for understanding and control of hydrogen relief process provides strong support. Finally, the recent electrocatalysts that enhance the catalytic performance of alkaline HER by hydrogen spillover effect are comprehensively sorted out and summarized. These findings not only demonstrate the practical value of hydrogen spillover under alkaline conditions, but also provide new directions for future design and optimization of electrocatalysts.
碱性水分离在工业规模制氢方面显示出巨大潜力。然而，其广泛应用仍然受到氢进化反应（HER）电催化剂性能的限制，在低过电位下很难达到理想的电流密度。利用氢溢出效应提高氢进化反应性能已成为一个新兴的研究方向。虽然以往的研究主要集中在酸性介质中的氢溢出，但最新研究表明，碱性条件下也存在氢溢出，其在提高 HER 性能方面的作用不容忽视。本文深入研究了酸性和碱性条件下氢溢出效应的特征差异，分析了两种不同环境下氢溢出的独特行为及其对催化过程的影响。同时总结了系统氢溢出表征方法，这些技术为理解和控制氢气泄放过程提供了有力支持。最后，对近年来利用氢溢出效应提高碱性 HER 催化性能的电催化剂进行了全面梳理和总结。这些发现不仅证明了氢溢出在碱性条件下的实用价值，也为未来电催化剂的设计和优化提供了新的方向。
{"title":"Application of Hydrogen Spillover in Alkaline Hydrogen Evolution Reaction","authors":"Zehui Yang, Shuyuan Pan, Fang Luo","doi":"10.1002/cctc.202401121","DOIUrl":"https://doi.org/10.1002/cctc.202401121","url":null,"abstract":"Alkaline water splitting has shown great potential for industrial‐scale hydrogen production. However, its wide application is still limited by the performance of hydrogen evolution reaction (HER) electrocatalysts, which are difficult to achieve ideal current density under low overpotential. Applying the hydrogen spillover effect to enhance HER performance has become an emerging research direction. Although previous studies mainly focused on hydrogen overflow in acidic media, the latest studies have shown that hydrogen overflow also exists under alkaline conditions, and its role in improving HER performance cannot be ignored. In this paper, the characteristic differences of the hydrogen overflow effect under acidic and alkaline conditions were investigated in depth, and the unique behavior of hydrogen overflow in the two different environments and its influence on the catalytic process were analyzed. System hydrogen spillover characterization methods are summarized at the same time, these technologies for understanding and control of hydrogen relief process provides strong support. Finally, the recent electrocatalysts that enhance the catalytic performance of alkaline HER by hydrogen spillover effect are comprehensively sorted out and summarized. These findings not only demonstrate the practical value of hydrogen spillover under alkaline conditions, but also provide new directions for future design and optimization of electrocatalysts.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141945553","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 electrocatalytic reduction of carbon dioxide by metal catalysts featuring dual‐atomic active sites, supported on two‐dimensional carbon‐nitrogen materials, holds promise for enhanced efficiency. The potential synergy between various support materials and transition metal compositions in influencing reaction performance has been recognized. However, systematic studies on the selection of optimal support materials remain limited, primarily due to the intricate structure of dual‐atom catalysts generating a variety of potential adsorption sites. Incorporating the influence of support materials further amplifies computational challenges, doubling the already substantial calculation requirements. This study addresses this challenge by introducing a machine learning approach to expedite the identification of the most stable intermediate adsorption sites and simultaneous prediction of adsorption energy. This innovative method significantly reduces computational costs, enabling the simultaneous consideration of active sites and support materials. We explore the use of both graphene‐like (g‐)C2N and g‐C9N4 materials, revealing their main distinction in the adsorption capacity for the intermediate *CHO. This variation is attributed to the different C:N ratios influencing support for the active site through distinct charge transfer conditions. Our findings offer valuable insights for the design and optimization of dual‐atom catalysts.
{"title":"Machine Learning‐Driven Selection of Two‐Dimensional Carbon‐Based Supports for Dual‐Atom Catalysts in CO2 Electroreduction","authors":"Zhen Tan, Xinyu Li, Yanzhang Zhao, Zhen Zhang, Javen Qinfeng Shi, Haobo Li","doi":"10.1002/cctc.202400470","DOIUrl":"https://doi.org/10.1002/cctc.202400470","url":null,"abstract":"The electrocatalytic reduction of carbon dioxide by metal catalysts featuring dual‐atomic active sites, supported on two‐dimensional carbon‐nitrogen materials, holds promise for enhanced efficiency. The potential synergy between various support materials and transition metal compositions in influencing reaction performance has been recognized. However, systematic studies on the selection of optimal support materials remain limited, primarily due to the intricate structure of dual‐atom catalysts generating a variety of potential adsorption sites. Incorporating the influence of support materials further amplifies computational challenges, doubling the already substantial calculation requirements. This study addresses this challenge by introducing a machine learning approach to expedite the identification of the most stable intermediate adsorption sites and simultaneous prediction of adsorption energy. This innovative method significantly reduces computational costs, enabling the simultaneous consideration of active sites and support materials. We explore the use of both graphene‐like (g‐)C2N and g‐C9N4 materials, revealing their main distinction in the adsorption capacity for the intermediate *CHO. This variation is attributed to the different C:N ratios influencing support for the active site through distinct charge transfer conditions. Our findings offer valuable insights for the design and optimization of dual‐atom catalysts.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141945555","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 Cover Feature of this issue highlights the work by Abir Kayal and Mrinmoy De, who describe a method for synthesizing recyclable organo-soluble MoS2 quantum dots (QDs) using a colloidal approach, which exhibits high efficiency as photocatalysts for the synthesis of biologically active α-amino phosphonates. The authors’ approach capitalizes on the oxidizing potential of molecular oxygen (O2). Specifically, MoS2 QDs are excited upon absorption of blue light, providing the necessary energy to initiate the formation of reactive iminium ion species from N-phenyl benzylamine, thereby facilitating product formation. Mechanistic analysis has underscored the critical role of MoS2 QDs in generating reactive superoxide radicals from O2 via single electron transfer (SET), highlighting their significance in this process. More information can be found in the Research Article by Abir Kayal and Mrinmoy De (DOI: 10.1002/cctc.202400264).
{"title":"Cover Feature: Organo-Soluble Colloidal MoS2 Quantum Dots (QDs) as an Efficient Photocatalyst for α-Amino Phosphonate Synthesis (ChemCatChem 15/2024)","authors":"Abir Kayal, Dr. Mrinmoy De","doi":"10.1002/cctc.202481502","DOIUrl":"https://doi.org/10.1002/cctc.202481502","url":null,"abstract":"<p>The <b>Cover Feature</b> of this issue highlights the work by Abir Kayal and Mrinmoy De, who describe a method for synthesizing recyclable organo-soluble MoS<sub>2</sub> quantum dots (QDs) using a colloidal approach, which exhibits high efficiency as photocatalysts for the synthesis of biologically active α-amino phosphonates. The authors’ approach capitalizes on the oxidizing potential of molecular oxygen (O<sub>2</sub>). Specifically, MoS<sub>2</sub> QDs are excited upon absorption of blue light, providing the necessary energy to initiate the formation of reactive iminium ion species from N-phenyl benzylamine, thereby facilitating product formation. Mechanistic analysis has underscored the critical role of MoS<sub>2</sub> QDs in generating reactive superoxide radicals from O<sub>2</sub> via single electron transfer (SET), highlighting their significance in this process. More information can be found in the Research Article by Abir Kayal and Mrinmoy De (DOI: 10.1002/cctc.202400264).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202481502","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980351","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}
Kaixin Chen, Jie Lin, Jiawei Guo, Haihong Chen, Jie Li
A highly 1,2-regioselective cobalt-catalyzed alkylarylation of conjugated dienes in a stereoretentive fashion has been disclosed. Indeed, the anion-coordination played a critical role for tuning the reactivity of arylzinc pivalates, thereby efficiently steering the cobalt-catalyzed three-component coupling reaction via radical relay pathway. Moreover, this protocol also distinguished by its mild conditions, ample substrate scope and good functional group compatibility.
{"title":"Modular 1,2-Selective Carboarylation of Conjugated Dienes under Cobalt Catalysis","authors":"Kaixin Chen, Jie Lin, Jiawei Guo, Haihong Chen, Jie Li","doi":"10.1002/cctc.202401063","DOIUrl":"https://doi.org/10.1002/cctc.202401063","url":null,"abstract":"A highly 1,2-regioselective cobalt-catalyzed alkylarylation of conjugated dienes in a stereoretentive fashion has been disclosed. Indeed, the anion-coordination played a critical role for tuning the reactivity of arylzinc pivalates, thereby efficiently steering the cobalt-catalyzed three-component coupling reaction via radical relay pathway. Moreover, this protocol also distinguished by its mild conditions, ample substrate scope and good functional group compatibility.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141945551","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}
Shoujie Zhang, Jiajie Ye, Jia Shen, Yanglong Guo, Wangcheng Zhan, Li Wang, Xuan Tang, Sheng Dai, Yun Guo
Direct oxidation of methane (DOM) under mild conditions is arguably one of the holy grails in chemistry. Cu‐based zeolite catalysts have attracted much attention for their high yield and selectivity of C1 oxygenates. However, the structure‐activity relationships of DOM remain controversial due to the complex configurations of Cu on zeolites. Herein, we prepared Cu/ZSM‐5 catalysts with various Cu loading and investigated the effects of Cu configurations on the DOM reaction. By combining the characterization techniques and evaluating the catalytic performance, we found that the configurations of Cu species could significantly affect the yield and distribution of C1 oxygenates, which was strongly dependent on Cu loading. The highly dispersed mononuclear CuII in the channels of ZSM‐5 is proved to be highly active. While the multinuclear Cu species inhibit the formation of HCOOH, simultaneously suppressing the overall reaction yield. The agglomerated CuO species on the surface of ZSM‐5 show a relatively low correlation with DOM reaction. Thus, the relationship between the yield of C1 oxygenates and Cu loading exhibits a typical volcanic curve and 2.2 wt.% Cu/ZSM‐5 possess the best performance using H2O2 as oxidant (productivity of 17,000 μmol gcat‐1 h‐1 with 98.6% selectivity at 50 °C).
在温和的条件下直接氧化甲烷（DOM）可以说是化学领域的圣杯之一。铜基沸石催化剂因其 C1 含氧化合物的高产率和高选择性而备受关注。然而，由于 Cu 在沸石上的复杂构型，DOM 的结构-活性关系仍存在争议。在此，我们制备了不同Cu负载量的Cu/ZSM-5催化剂，并研究了Cu构型对DOM反应的影响。通过结合表征技术和催化性能评估，我们发现 Cu 物种的构型会显著影响 C1 含氧化合物的产率和分布，而这与 Cu 的负载量密切相关。事实证明，ZSM-5 通道中高度分散的单核 CuII 具有很高的活性。多核 Cu 物种抑制了 HCOOH 的形成，同时抑制了整体反应产率。ZSM-5 表面的团聚 CuO 物种与 DOM 反应的相关性相对较低。因此，C1 含氧化合物的产率与 Cu 负载之间的关系呈现出典型的火山曲线，使用 H2O2 作为氧化剂，2.2 wt.% Cu/ZSM-5 的性能最佳（50 °C 时的产率为 17,000 μmol gcat-1 h-1，选择性为 98.6%）。
{"title":"Direct Oxidation of Methane to C1 Oxygenates on Cu/ZSM‐5: Reaction Property and Configuration of Cu species","authors":"Shoujie Zhang, Jiajie Ye, Jia Shen, Yanglong Guo, Wangcheng Zhan, Li Wang, Xuan Tang, Sheng Dai, Yun Guo","doi":"10.1002/cctc.202401137","DOIUrl":"https://doi.org/10.1002/cctc.202401137","url":null,"abstract":"Direct oxidation of methane (DOM) under mild conditions is arguably one of the holy grails in chemistry. Cu‐based zeolite catalysts have attracted much attention for their high yield and selectivity of C1 oxygenates. However, the structure‐activity relationships of DOM remain controversial due to the complex configurations of Cu on zeolites. Herein, we prepared Cu/ZSM‐5 catalysts with various Cu loading and investigated the effects of Cu configurations on the DOM reaction. By combining the characterization techniques and evaluating the catalytic performance, we found that the configurations of Cu species could significantly affect the yield and distribution of C1 oxygenates, which was strongly dependent on Cu loading. The highly dispersed mononuclear CuII in the channels of ZSM‐5 is proved to be highly active. While the multinuclear Cu species inhibit the formation of HCOOH, simultaneously suppressing the overall reaction yield. The agglomerated CuO species on the surface of ZSM‐5 show a relatively low correlation with DOM reaction. Thus, the relationship between the yield of C1 oxygenates and Cu loading exhibits a typical volcanic curve and 2.2 wt.% Cu/ZSM‐5 possess the best performance using H2O2 as oxidant (productivity of 17,000 μmol gcat‐1 h‐1 with 98.6% selectivity at 50 °C).","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141945483","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}
Marcos López-Aguilar, Marina Ramos-Martín, Dr. Nicolás Ríos-Lombardía, Dr. Luciana Cicco, Dr. Joaquín García-Álvarez, Dr. Carmen Concellón, Dr. Vicente del Amo
The Front Cover represents an sterodivergent and direct “chemical production chain” capable of converting simple primary alcohols into highly-substituted asymmetric aldols through the fruitful combination of an aerobical and chemoselective Cu-catalyzed oxidation of primary alcohols with a concomitant and compatible enantio- and diastereoselective cross aldol reaction catalyzed by a binary guanidium salt/(S)-proline system, working under bench-type reaction conditions and in the absence of any external organic solvent. More information can be found in the Research Article by J. García-Álvarez, C. Concellón, V. del Amo, and co-workers (DOI: 10.1002/cctc.202400437).
封面介绍了一种立体定向和直接的 "化学生产链"，它能够将简单的伯醇转化为高度取代的不对称醛醇，具体方法是将铜催化的伯醇有氧化学选择性氧化反应与胍盐/(S)-脯氨酸二元体系催化的对映和非对映选择性交叉醛醇反应富有成效地结合起来，在台式反应条件下进行，并且不需要任何外部有机溶剂。更多信息，请参阅 J. García-Álvarez、C. Concellón、V. del Amo 及合作者的研究文章（DOI: 10.1002/cctc.202400437）。
{"title":"Front Cover: Synergistic One-pot Tandem Combination of Cu and Proline Catalysis: Stereodivergent Synthesis of Chiral Aldols from Primary Alcohols (ChemCatChem 15/2024)","authors":"Marcos López-Aguilar, Marina Ramos-Martín, Dr. Nicolás Ríos-Lombardía, Dr. Luciana Cicco, Dr. Joaquín García-Álvarez, Dr. Carmen Concellón, Dr. Vicente del Amo","doi":"10.1002/cctc.202481501","DOIUrl":"https://doi.org/10.1002/cctc.202481501","url":null,"abstract":"<p>The <b>Front Cover</b> represents an sterodivergent and direct “<i>chemical production chain</i>” capable of converting simple primary alcohols into highly-substituted asymmetric aldols through the fruitful combination of an aerobical and chemoselective Cu-catalyzed oxidation of primary alcohols with a concomitant and compatible enantio- and diastereoselective cross aldol reaction catalyzed by a binary guanidium salt/(<i>S</i>)-proline system, working under bench-type reaction conditions and in the absence of any external organic solvent. More information can be found in the Research Article by J. García-Álvarez, C. Concellón, V. del Amo, and co-workers (DOI: 10.1002/cctc.202400437).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202481501","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980350","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}
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