ChemCatChem最新文献

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The effect of dithionite and its decomposition products on redox mediators used in the cyclic voltammetry of nitrogenase enzymes 连二亚硫酸盐及其分解产物对用于氮酶循环伏安法的氧化还原介质的影响

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-20 DOI: 10.1002/cctc.202400595

Jessica K Bilyj, Christina Gregg, Craig C Wood, Trevor Rapson

Cyclic voltammetry is a powerful tool to study enzyme mechanisms. Over the last decade voltammetry has been applied to probe aspects of nitrogenase catalysis. One aspect that is often overlooked is the effect of dithionite (S2O42-, DTH) that is routinely added to purification and storage buffers to protect nitrogenase and anaerobic enzymes alike (e.g hydrogenase) from oxygen. Dithionite has extremely complex chemistry with a myriad of decomposition products. Here we sought to systematically investigate the effect of dithionite and some of its decomposition products on the voltammetry of different redox mediators independently and in conjunction with nitrogenase. We found the major decomposition product sulfite (SO32-) gives rise to reductive catalysis, which cannot be distinguished from enzyme catalysis, particularly with cobaltocenium mediators. We provide recommendations on how to identify and avoid interpreting ‘pseudo’ catalysis in lieu of enzyme catalysis by DTH and reinforce the requirement to remove DTH prior to performing cyclic voltammetry experiments.

循环伏安法是研究酶机制的有力工具。在过去的十年中，伏安法已被用于探测氮酶催化的各个方面。其中一个经常被忽视的方面是连二亚硫酸盐（S2O42-，DTH）的影响，连二亚硫酸盐通常被添加到纯化和储存缓冲液中，以保护氮酶和厌氧酶（如氢酶）免受氧气的影响。连二亚硫酸盐的化学性质极其复杂，分解产物不计其数。在此，我们试图系统地研究连二亚硫酸盐及其一些分解产物对不同氧化还原介质伏安法的影响，包括独立影响和与氮酶结合影响。我们发现，主要分解产物亚硫酸盐（SO32-）会产生还原催化作用，而这种催化作用无法与酶催化作用区分开来，尤其是在钴硒介质中。我们就如何通过 DTH 识别和避免解释 "伪 "催化作用以代替酶催化作用提出了建议，并强调了在进行循环伏安法实验之前去除 DTH 的要求。

引用次数: 0

Synergetic effect of Ni-CeO2 bimetallic catalyst for an effective decomposition of methane to hydrogen and filamentous nanocarbons Ni-CeO2 双金属催化剂在将甲烷有效分解为氢气和丝状纳米碳方面的协同效应

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-20 DOI: 10.1002/cctc.202400700

Adeel Ahmad, Iqra Reyaz Hamdani, Abdul Rasheed Pillantakath, Ahmed Al Shoaibi, srinivasakannan chandrasekar, Mohammad Mozahar Hossain

The work attempts to synthesis nickel-ceria bimetallic catalysts supported on porous carbon template, thermally stable at 850 °C, for dehydrogenation of methane to hydrogen and carbon nanostructures. A series of bimetallic Ni catalysts were synthesized by varying the % ceria content (30Ni-5CeO2/AC, 30Ni-10Ce O2/AC, and 30Ni-15CeO2/AC) using the incipient wetness impregnation approach. Among the set of bimetallic catalysts, the 30Ni-5CeO2/AC catalyst was found to offer highest methane conversion and stability. A maximum conversion of 90% was achieved with 40% methane feed concentration along with good catalyst stability. The promoter ceria at low concentration enhanced the dispersion of metal over the catalytic surface, resulting in adequate metal-support interaction. The ability of the carbon support along with promoter ceria enhanced the thermal stability of the Ni catalyst up to 850 °C, offering high conversion and catalyst stability has been the highlight of the work. Advanced analytical techniques were used to characterize the catalyst's structural, textural, and morphological properties both before and after the reaction. The morphological study of the best-performing catalyst demonstrated the formation of dense carbon nanotubes through tip-growth mechanism exhibiting a high aspect ratio.

该研究试图合成在多孔碳模板上支撑的镍铈双金属催化剂，其在 850 ℃ 下具有热稳定性，用于将甲烷脱氢为氢气和碳纳米结构。通过改变铈的含量（30Ni-5CeO2/AC、30Ni-10Ce O2/AC 和 30Ni-15CeO2/AC），采用萌发湿法浸渍合成了一系列双金属镍催化剂。在这组双金属催化剂中，30Ni-5CeO2/AC 催化剂的甲烷转化率和稳定性最高。在甲烷进料浓度为 40% 的情况下，甲烷转化率最高可达 90%，而且催化剂稳定性良好。低浓度的促进剂铈增强了金属在催化表面的分散，从而产生了充分的金属-支撑相互作用。碳载体和促进剂铈能够增强镍催化剂的热稳定性，最高温度可达 850 °C，从而提供了高转化率和催化剂稳定性，这也是这项工作的亮点。研究人员采用先进的分析技术对催化剂在反应前后的结构、质地和形态特性进行了表征。对性能最好的催化剂进行的形态学研究表明，通过尖端生长机制形成的致密碳纳米管具有很高的纵横比。

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引用次数: 0

One-pot synthesis of (S)-flavanones by a double-face promiscuous chemo-enzymatic cascade of lipases. 通过脂肪酶双面杂化酶级联法一次性合成(S)-黄烷酮。

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-20 DOI: 10.1002/cctc.202400974

Eliana Capecchi, Valentina Ubertini, Elisabetta Tomaino, Davide Piccinino, Elisa De Marchi, Bruno Mattia Bizzarri, Giovanni Carotenuto, Tiziana Castrignanò, Raffaele Saladino

The one-pot stereoselective synthesis of (S)-flavanones from 2’-hydroxyacetophenone and substituted aromatic aldehydes was obtained by a double-face promiscuous chemo-enzymatic cascade of porcine pancreas and Mucor javanicus lipases.The reaction pathway comprises: A) cross-aldol condensation catalysed by porcine pancreas lipase to yield chalcone intermediates; B) unprecedented intramolecular oxa-Michael addition of chalcone intermediates to (S)-flavanones. Mucor javanicus lipase was the most effective enzyme in step B. Imidazole and 2-methylimidazole were studied as additive in order to improve the efficacy of the overall transformation. The sustainability of the chemo-enzymatic cascade was increased by immobilization of lipases on cross-linked hydroxy-methylated kraft lignin nanoparticles, by use of concanavalin A. Immobilization conferred considerable stability and reusability at the system for 4 runs. Noteworthy, the reaction mixture was significantly enriched in (S)-flavanones under both homogeneous and heterogeneous conditions. Computational studies encompassing docking and molecular dynamic analyses showed the role played by evolutionary conserved oxyanion holes and catalytic triad of Mucor javanicus lipase in the stereocontrol of the intra-molecular oxa-Michael addition.

通过猪胰腺脂肪酶和Mucor javanicus脂肪酶的双面杂化酶级联反应，从2'-羟基苯乙酮和取代的芳香醛中获得了(S)-黄烷酮的单锅立体选择性合成：A) 在猪胰脂肪酶的催化下进行交醛缩合，生成查尔酮中间体；B) 查尔酮中间体与(S)-黄烷酮发生前所未有的分子内氧杂迈克尔加成反应。为了提高整个转化过程的效率，研究人员研究了咪唑和 2-甲基咪唑作为添加剂。使用 concanavalin A 将脂肪酶固定在交联的羟甲基化牛皮纸木质素纳米颗粒上，提高了化学酶级联的可持续性。值得注意的是，在均相和异相条件下，反应混合物中的（S）-黄烷酮都明显富集。包括对接和分子动力学分析在内的计算研究表明，在分子内氧杂迈克尔加成的立体控制过程中，进化保守的氧阴离子孔和粘孢子脂肪酶的催化三要素发挥了作用。

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引用次数: 0

Gold Catalysts for Selective Hydrogenations: The Role of Heterolytic H2 Dissociation 选择性加氢的金催化剂：异解氢解离的作用

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-19 DOI: 10.1002/cctc.202400207

Jhonatan Luiz Fiorio, Raíza Rosa Garcia Guerra, Belén Martin-Matute, Liane Marcia Rossi

Hydrogenations are fundamental transformations in organic synthesis, and the industrial applications span from food, petrochemical, fine chemicals to pharmaceuticals synthesis where hydrogenations of multifunctional molecules should be carried out in a chemoselective way. In this concept article we aim at providing an overview on the activation of molecular hydrogen (H2) via heterolytic dissociation, which is responsible to unlock high activity of gold catalysts for chemoselective hydrogenations. The key benefit of heterolytically dissociated H species is their preference for hydrogenating polar unsaturated groups like C=O, C=N, and C=S, as these polar bonds are ideal acceptors for proton and hydride pairs. We will provide examples on how to obtain enhanced chemoselectivity on alkynes, a, b-unsaturated aldehydes and nitro-compounds hydrogenations with gold catalysts.

加氢反应是有机合成中的基本转化过程，其工业应用领域包括食品、石油化工、精细化工和医药合成，其中多功能分子的加氢反应必须以化学选择的方式进行。在这篇概念文章中，我们旨在概述通过杂解离解激活分子氢（H2）的方法，这是金催化剂在化学选择性加氢反应中释放高活性的原因。异解氢的主要优点是它们偏好氢化 C=O、C=N 和 C=S 等极性不饱和基团，因为这些极性键是质子和氢化物对的理想接受体。我们将举例说明如何利用金催化剂提高炔、a、b-不饱和醛和硝基化合物氢化的化学选择性。

引用次数: 0

A Radical Revolution in the 21st Century 21 世纪的激进革命

IF 3.8 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-14 DOI: 10.1002/cctc.202401079

Dr. Adrián Gómez-Suárez, Prof. Spence P. Pitre, Prof. Chen Zhu

This Special Collection on “Radical Chemistry in Homogeneous Catalysis and Organic Synthesis” organized in collaboration with the European Journal of Organic Chemistry and ChemCatChem showcases the maturity of field. Overall, this Special Collection encompasses 11 reviews and 27 research articles, covering a diverse range of topics. It presents the latest advancements in the controlled generation of radical species using transition metal catalysis, photoredox catalysis, or electrochemistry. It highlights the importance of moving towards more sustainable chemical processes, with particular focus on the development of novel organo(photo)catalysts, or efficient catalyst-free reactions. It presents new transformations to access complex scaffolds as well as new building blocks and reagents, further simplifying single-electron disconnection logic. In addition, it also highlights the key advancements in addressing some of the current challenges in radical chemistry, such the development of enantioselective reactions or how to scale-up radical processes to meet the needs of the fine chemical industry.

与《欧洲有机化学杂志》（European Journal of Organic Chemistry）和 ChemCatChem 合作出版的 "均相催化和有机合成中的自由基化学 "特辑展示了该领域的成熟度。总体而言，本特辑包括 11 篇综述和 27 篇研究文章，涵盖了不同的主题。它介绍了利用过渡金属催化、光氧化催化或电化学控制自由基生成的最新进展。它强调了向更可持续的化学过程发展的重要性，尤其关注新型有机（光）催化剂或高效无催化剂反应的开发。它介绍了获得复杂支架的新转化以及新的构建模块和试剂，进一步简化了单电子断开逻辑。此外，该书还重点介绍了在解决当前自由基化学面临的一些挑战方面取得的主要进展，如开发对映体选择性反应或如何放大自由基工艺以满足精细化工行业的需求。

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引用次数: 0

Smart Materials for Biocatalysis Regulation through Thermoresponsive Polymers 通过热致伸缩聚合物调节生物催化的智能材料

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-12 DOI: 10.1002/cctc.202400699

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.

温度响应型生物催化杂化材料具有多种优势，如稳定性更好、催化效率更高、生物催化剂寿命更长。以策略性的方式将酶与热致伸缩性聚合物相结合，可以更智能地调节酶的活性以应对温度变化。热致伸缩材料可作为酶的保护屏障，或根据温度变化控制酶的暴露和释放，从而扩大酶在各种环境中的应用。本综述旨在全面介绍具有热致伸缩特性的酶-聚合物杂化材料的设计策略，并探讨合理控制生物催化系统所涉及的优势、应用和挑战。该研究强调了创造刺激响应型生物催化杂化材料的重要性，这些材料可用于从可控药物递送到工业催化等各种应用领域。此外，我们还概述了这一领域的主要研究机会和未来研究前景。

引用次数: 0

Decomposition of N2O by Ruthenium Catalysts – RuO2 as Active Phase on Non‐Reducible Supports 钌催化剂分解 N2O - 非还原性载体上的活性相 RuO2

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-12 DOI: 10.1002/cctc.202400347

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.

钌已被支撑在特定选择的非还原支撑物（Al2O3、SiO2、Al2O3-SiO2 混合氧化物、Mg/ZnAl2O4 尖晶石和 AlF3）上，这些催化剂已在氧化亚氮（N2O）的分解过程中进行了测试，以确定钌的催化活性相。为了进行比较，还合成并研究了纯净的块状二氧化钌 RuO2 和分离的 Ru 表面络合物。催化剂的表征方法包括 X 射线衍射、H2 化学吸附、N2 物理吸附、温度编程还原和解吸 TPR/TPD）以及原位红外光谱（IR）。所有目的实验都强烈表明，N2O 的分解发生在二氧化钌（RuO2）上，而不是金属颗粒上。H2 预还原成金属 Ru 对所有含氧支持物都有抑制作用。活性随着氧化钌的分散而增加。块状二氧化钌的催化性能最好。

引用次数: 0

Application of Hydrogen Spillover in Alkaline Hydrogen Evolution Reaction 氢溢出在碱性氢进化反应中的应用

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-12 DOI: 10.1002/cctc.202401121

Zehui Yang, Shuyuan Pan, Fang Luo

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。

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引用次数: 0

Machine Learning‐Driven Selection of Two‐Dimensional Carbon‐Based Supports for Dual‐Atom Catalysts in CO2 Electroreduction 机器学习驱动的二氧化碳电还原双原子催化剂的二维碳基载体选择

IF 4.5 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-12 DOI: 10.1002/cctc.202400470

Zhen Tan, Xinyu Li, Yanzhang Zhao, Zhen Zhang, Javen Qinfeng Shi, Haobo Li

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.

以二维碳氮材料为支撑、具有双原子活性位点的金属催化剂对二氧化碳进行电催化还原，有望提高效率。各种支撑材料和过渡金属成分在影响反应性能方面的潜在协同作用已得到认可。然而，有关最佳支撑材料选择的系统研究仍然有限，这主要是由于双原子催化剂结构复杂，会产生各种潜在的吸附位点。考虑到支撑材料的影响，进一步加大了计算难度，使本已十分庞大的计算需求翻了一番。为了应对这一挑战，本研究引入了机器学习方法，以加快识别最稳定的中间吸附位点，并同时预测吸附能量。这种创新方法能同时考虑活性位点和支撑材料，大大降低了计算成本。我们探索了类石墨烯（g-）C2N 和 g-C9N4 材料的使用，发现了它们在中间体 *CHO 吸附能力上的主要区别。这种差异归因于不同的 C:N 比率通过不同的电荷转移条件影响了对活性位点的支持。我们的研究结果为双原子催化剂的设计和优化提供了宝贵的见解。

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引用次数: 0

Cover Feature: Organo-Soluble Colloidal MoS2 Quantum Dots (QDs) as an Efficient Photocatalyst for α-Amino Phosphonate Synthesis (ChemCatChem 15/2024) 封面专题：有机可溶胶体 MoS2 量子点 (QDs) 作为 α-氨基膦酸盐合成的高效光催化剂（ChemCatChem 15/2024）

IF 3.8 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem

Pub Date : 2024-08-12 DOI: 10.1002/cctc.202481502

Abir Kayal, Dr. Mrinmoy De

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).

本期封面特写重点介绍了 Abir Kayal 和 Mrinmoy De 的研究成果，他们介绍了一种利用胶体方法合成可回收有机可溶 MoS2 量子点 (QDs) 的方法，该方法作为光催化剂可高效合成具有生物活性的 α-氨基膦酸盐。作者的方法利用了分子氧（O2）的氧化潜能。具体来说，MoS2 QDs 在吸收蓝光时被激发，提供必要的能量，启动 N-苯基苄胺中活性亚胺离子物种的形成，从而促进产物的形成。机理分析强调了 MoS2 QDs 通过单电子转移 (SET) 从 O2 生成活性超氧自由基的关键作用，突出了它们在这一过程中的重要性。更多信息请参阅 Abir Kayal 和 Mrinmoy De 的研究文章（DOI: 10.1002/cctc.202400264）。

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引用次数: 0

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