This article is part of the Bridging the Gaps: Learning from Catalysis across Boundaries special issue. Catalysis is a central science that will have a key contribution to the development of more sustainable processes, in connection with the current emerging and yet urgent societal challenges related to climate change and environmental concerns. Traditionally, catalysis has been subdivided into three fields: heterogeneous catalysis, homogeneous catalysis, and biocatalysis, and it can also be classified in terms of thermo-, electro-, and photocatalytic processes within the three fields. These disciplines have been developed mostly independently to address specific scientific and distinct catalytic challenges. As catalysis is a molecular phenomenon where bonds are broken and formed on catalytic active sites, there is no doubt about the importance of local structures. However, it has been recognized over the years that dynamics and long-range interactions are often equally important for catalyst design and for rationalizing overall catalytic performances across all types of catalysts. In recent years, cross-fertilization between these distinct fields and complementary hybrid approaches to catalyst design have begun to address some of the inherent limitations of the traditional fields. These efforts have enabled combining some of the most attractive features of the disciplines. As both members of the NCCR Catalysis, a Swiss-wide effort aiming at developing more sustainable catalytic processes, we have been particularly interested in assembling a collection of 21 review articles that summarize the state-of-the-art of catalysis across boundaries in this thematic issue of Chemical Reviews coined “Bridging the Gaps: Learning from Catalysis across Boundaries”. The temporal delivery or removal of photons, electrons, and protons is a hallmark of photosynthesis. Although Nature has mastered such highly cross-regulated processes through the course of evolution, mimicking such complex photocatalytic processes remains extremely challenging, with either homogeneous or heterogeneous catalysts. In a biomimetic spirit, compartmentalization of the catalytic components within a confined environment enables a high degree of spatial organization, combined with a timely and directional delivery or removal of reagents and products. In their review, Pullen, Reek and co-workers summarize the state-of-the-art in the field of artificial photosynthesis and photocatalysis within supramolecular coordination cages. An alternative means of minimizing mutual inhibition─often observed in reaction cascades─relies on compartmentalizing the incompatible catalytic partners. Two reviews provide complementary perspectives on the strategies aiming at combining homogeneous and heterogeneous catalysts and biocatalysts for the synthesis of high-added-value products: Gröger, Lipschutz and Gallou as well as Lavandera, Gotor-Fernández and co-workers. With the aim of minimizing isolation- and purification-steps during multistep syntheses, concurrent catalytic cascades have attracted increasing attention. As enzymes have evolved to operate in complex cellular media, they excel at catalyzing such complex tasks. However, their reaction repertoire is rather limited. To overcome this limitation, efforts have been directed at combining homogeneous catalysts with enzymes for chemoenzymatic concurrent cascades. However, this has proven challenging as both enzymes and homogeneous catalysts often suffer from mutual inhibition. To circumvent this problem, various compartmentalization strategies have been pursued to enable concurrent cascades. These include sequential catalysis─as a form of “time compartmentalization”─biphasic media, MOFs, zeolites, heterogeneous catalysts, PDMS-thimbles and membranes, alginate beads, as well as nonionic surfactants, etc. Importantly for the nonexpert reader, the authors provide a lucid discussion of the challenges and limitations of these compartmentalization strategies. To complement traditional enzyme immobilization and compartmentalization strategies, Metal–Organic Frameworks (MOFs) have attracted increasing attention as versatile and highly organized hosts for the encapsulation of enzymes. Shi, Zhou and co-workers present an insightful perspective on (i) the synergistic interplay between enzymes and MOFs as well as (ii) the assembly and catalytic potential of bioinspired MOFs. Another layer of complexity is introduced with electrocatalysis, which requires compartmentalization and recycling of NADPH and ATP to minimize energetic cost. To maintain its complex network of out-of-equilibrium reaction networks essential to life, the metabolism relies on ATP and NAD(P)H as energy currency. In the spirit of the circular economy, spent ATP and NAD(P)⁺ are continuously recycled within a cell. In their review, Armstrong, Megarity and co-workers summarize their efforts to recapitulate such Life-like features in a confined electrocatalytic setting that they coined the electrochemical Leaf (e-Leaf). The extension of protein film electrochemistry to reversible electrochemical regeneration of NAD(P)H by ferredoxin-NADP⁺ reductase (FNR), immobilized in the pores of a nanostructured indium tin oxide film, has enabled enzyme-cascade electrocatalysis. For the recycling of spent ATP, they rely on a kinase pair that is also immobilized in the ITO nanopores. The authors discuss various enzyme cascade networks that have been implemented in the e-Leaf. A milestone in this field is a four-enzyme linear cascade. Nanoconfinement of FNR, the malic enzyme, fumarase, and l-aspartate ammonia lyase enables the electrochemical conversion of pyruvate and CO₂ to aspartate, combined with the regeneration of NADPH which is required to fix CO₂ to pyruvate. In a biomimetic spirit, electrocatalysis enables driving of such enzymatic cascades in both directions, depending on the applied potential. This work summarizes the groundbreaking work in engineering a versatile electrocatalytic platform to assemble complex enzyme cascades and investigate complex catalytic networks reminiscent of the metabolism. With the aim of expanding the scope of biocatalysis to reactions involving photogenerated excited state intermediates, photobiocatalysis has attracted increasing attention in the past 25 years. Throughout their review, Hyster and co-workers identify and provide a deep insight into four types of photobiocatalytic systems that have been reported to date: (i) photoenzymatic catalysis, (ii) synergistic photoenzymatic catalysis, (iii) tandem photocatalysis–enzyme reactions, and (iv) enzymatic reactions coupled to natural photosynthesis. Both mechanistic considerations and the great synthetic potential of the newly accessible reactions are summarized to highlight untapped opportunities in the field. A living cell, including its various organelles, can be viewed as the ultimate molecular factory, enabling the orchestration of exquisitely cross-regulated reaction networks. In 1973, Cohen and Bailey pioneered recombinant DNA technology. This milestone opened the fascinating perspective of converting cells into molecular factories for the overproduction of high-added-value chemicals (insulin, artemisinic acid, etc.) or biofuels. The review by Zhao and co-workers summarizes the state-of-the-art in the field of metabolic engineering. The authors critically analyze the widely applied strategy to maximize the production of a targeted compound within an engineered host organism: Design, Build, Test, and Learn. The field has witnessed significant growth in the past 30 years, thanks to breakthroughs in various fields including: PCR technology, directed evolution, CRISPR-cas9, proteomics, metabolomics, machine learning, etc. Although glucose typically serves as carbon source, it is highly desirable to rely on cheaper alternatives. Accordingly, recent efforts strive to rely on: plastic-deconstruction, methanol, CO, CO₂, etc. The authors provide convincing arguments that metabolic engineering offers a sustainable alternative to conventional petroleum-based production processes. The main technical bottleneck seems to be the lack of access to facilities for large-scale production. One of the main features of using cells as molecular factories to produce a compound (phenotype) of interest is the phenotype–genotype linkage, thus enabling a straightforward identification of the improved enzyme mutant (genotype). To fully capitalize on the impressive developments in automated DNA synthesis and next-generation sequencing necessitates ultrahigh throughput screening tools. In their authoritative review, Hollfelder and co-workers summarize the state-of-the-art in droplet microfluids, combined with NGS and deep learning algorithms for the optimization of biocatalysts. Encapsulation within droplets maintains the phenotype–genotype linkage and enables screening routinely >10⁷ variants. Recent developments include the use of label-free detection methods, including mass spectroscopy. 2020 marked the one-hundredth anniversary of Staudinger’s first publication on polymers. In the past century, the use of man-made polymers has grown continuously, and it is predicted to reach 700 million tons per year in 2030. Alarmingly, 80% of these polymers end up in landfills, and only <20% are recycled. In the spirit of the circular economy, polymers represent an untapped source of building blocks. In their thorough review, Taton, Marty, André and co-workers summarize the state-of-the-art in the field of biocatalytic solutions to plastic recycling and upcycling. They provide convincing arguments that enzymatic degradation of PET and PLA has reached a high degree of maturity, while all carbon polymers remain challenging to deconstruct enzymatically. The catalytic reduction of CO₂ requires the timely delivery of multiple reagents. Mastering this highly challenging reaction is key to reducing our carbon footprint. Several complementary catalytic strategies are being developed toward CO₂ fixation and are summarized in this thematic issue. Although it is likely the most ancient source of carbon on the planet, relying on CO₂ as (sole) carbon source currently represents a Holy Grail in synthetic biology. In their review, Winkler, Tinzl, Glueck and co-workers provide a comprehensive overview of (de)carboxylating enzymes and their potential for biotechnological applications. After presenting the thermodynamic challenges associated with carboxylation reactions and strategies used to drive the reaction toward the formation of C–C bonds, the authors present all known naturally occurring (de)carboxylases, the (artificial) pathways they are associated with, as well as the energetic cost associated with each CO₂-fixation step (i.e., ATP, NAD(P)H, etc.). The review ends with a discussion on the prospects of engineering more efficient (artificial) CO₂-fixing pathways and their potential socioeconomic consequences. One of the strategies to improve chemoenzymatic carboxylation cascade reactions may be the design of highly efficient artificial CO₂-fixing enzymes. In this context, the Fischer–Tropsch heterogeneous-catalytic process enables the conversion of carbon monoxide and hydrogen into liquid hydrocarbons. As carbon monoxide is isoelectronic with dinitrogen, it has been widely used as a substrate-surrogate in the context of nitrogenase-related mechanistic studies. Strikingly, Ribbe, Hu and co-workers reported in 2010 that the vanadium-containing nitrogenase from Azobacter vinilandii catalyzes the conversion of CO or even CO₂ to short hydrocarbons. This finding opened fascinating perspectives for the carbon-neutral conversion of either CO or CO₂ into hydrocarbons. The individual subunits of nitrogenase, the isolated cofactors, as well as synthetic cofactor mimics─including [(RS)₄Fe₄S₄]─produce a larger product distribution and catalyze the reduction of CO, CO₂, and CN^– to C₁–C₇ hydrocarbons. In stark contrast to the energy-demanding Fischer–Tropsch process, these enzymatic or (RS)₄Fe₄S₄-catalyzed reactions proceed under ambient conditions and utilize H⁺ and sacrificial e^– donors. These findings are not only interesting for biotechnological applications but might have evolutionary relevance concerning primordial processes of carbon fixation. The Fischer–Tropsch (FT) process is indeed a prototypical example illustrating the beauty and the complexity of heterogeneous catalysis, where C–O bonds are broken and C–C bonds are formed to generate higher hydrocarbons or alcohols upon the hydrogenation of usually CO. Saeys and co-workers summarize the state-of-the-art in this field, focusing on how surface science and microkinetic and computational modeling provide a molecular-level understanding of the reactive state and reaction mechanism in FT catalysts. As illustrated above, in contrast to molecular catalysts or even enzymes, these systems are difficult to describe at the molecular level, including highly debated and unknown active sites. These are often generated in situ from the reactants and the already complex objects, such as the supported nanoparticles used in the FT. This has pushed the field in several directions involving bottom-up to top-bottom synthetic approaches, building model systems, and developing advanced spectroscopic techniques. When addressing the development of more selective and robust catalysts based on metallic nanoparticles, one approach has been to look into introducing additional elements; the formation of alloys modifies the nature of surface sites, by avoiding the formation of large ensembles and/or by changing the electronic nature of the nanoparticles or reactive metal sites. Furukawa and co-worker have succeeded in critically analyzing the field of metal alloys; following a classification of metal alloys and various terminology, the review discusses catalyst design and then illustrates the use of metal alloys in numerous catalytic applications, from classical hydrogenation/dehydrogenation reactions to deNO_x and electrocatalytic processes. To understand these complex objects, Zheng and co-workers discuss in their review how atomically dispersed metal catalysts and ligand-protected atomically precise metal clusters can contribute to model and better understand heterogeneous catalysts, allowing the description of local coordination at metal–support interfaces and how ligands can affect the reactivity of metal sites. At the other end, Gross and co-workers review how high spatial resolution microscopy and spectroscopy can provide molecular-level insights about the interaction of ligands and surfaces down to the single particles. While large objects, zeolites are often regarded as ideal heterogeneous catalysts, where the crystalline nature of the oxide lattice provides ways to generate well-defined metal sites, incorporated with the microcrystalline structure of these materials. In addition, they offer well-defined cavities (compartments to resonate with the discussion above) to host not only the active sites, but also large objects such as clusters and nanoparticles. In this context, Yu and co-workers discuss zeolites in great detail, from the classification and the dynamics of active sites to synthetic and characterization methodologies, as well as their applications in numerous processes. Furthermore, Chizallet and co-workers show how zeolites, through the detailed understanding of their active site structure and microporous environment thanks to a combination of advanced spectroscopic and computational approaches, lie at the crossroad of heterogeneous and molecular catalysis. Bridging the gap between the microporous and molecular worlds, Dincǎ and co-workers looked into the corresponding Metal–Organic-Frameworks (MOFs), revealing the assets of these unique solid-state structures with molecularly defined frameworks. Similarly, isolated sites can also be found on extended surfaces such as nitrogen-doped carbons. These materials allow hosting highly dispersed metal sites, often referred to as single atom catalysts. These materials can be viewed as ideal systems, enabling bridging the gap between homogeneous and heterogeneous catalysis but also understanding at the fundamental level redox processes in catalysis because of the conductive nature of these supports. In their review, Bates, Stahl and co-workers draw a unique parallel between aerobic oxidation reactions and oxygen-reduction electrocatalysis, further illustrating how one can transfer concepts from electrocatalysis to thermal catalysis. To complement this, Patzke and co-workers discuss how in situ/operando characterization techniques have enabled monitoring catalysts for the multielectron processes involved in the oxygen evolution (OER) and reduction (ORR) reactions. The review also highlights how monitoring under relevant conditions enables the development of strategies to interrogate restructuration processes, for instance. Finally, to illustrate some important challenges in catalysis Hutchings and co-workers review one of the Holy Grails of chemistry, with a discussion of catalyst development for the selective oxidation of methane. This field highlights the specific challenges of each field and illustrates how cross-fertilization between the three classes of catalysts can help to design better catalysts. We hope you will enjoy reading this collection of review articles and upcoming ones related to catalysis across boundaries. Thomas R. Ward obtained his PhD from the ETHZ, working with Profs. Venanzi and Seebach on C₃-symmetric ligands and their use in homogeneous catalysis. He then joined Prof. Roald Hoffmann at Cornell University for his postdoc. In collaboration with Ford Motors, they modeled and rationalized the versatility of oxide-supported precious metals for the reduction of NO in the three-way catalyst. Upon returning to Switzerland, he focused on the development of artificial metalloenzymes. Such hybrid catalysts bridge the gap between homogeneous and enzymatic catalysis. Since 2008, he has been full professor at the University of Basel and associated with the Swiss National Competence Center in Catalysis, aiming at establishing Switzerland as an internationally recognized center for sustainable chemistry research, education, and innovation. Christophe Copéret (CCH) obtained his PhD at (Purdue University, USA) with Prof. E. i. Negishi, where he investigated the synthesis of complex molecules via Pd-catalyzed carbonylation reactions. After a postdoctoral stay with Prof. K. B. Sharpless (The Scripps Research Institute), CCH was offered a research position at CNRS in 1998 and was promoted to CNRS Research Director in 2008. Since 2010, CCH has been Professor in the Department of Chemistry and Applied Biosciences, ETH Zürich. His scientific interest lies at the frontiers of molecular, material and surface chemistry as well as NMR spectroscopy with the aim to design molecularly defined solid catalysts through detailed mechanistic studies and structure–activity relationships. CCH is currently coordinating together with Prof. R. Buosanti (EPFL) the effort related to Tools in the Swiss National Competence Center in Catalysis, and he has been an Associate Editor for the Journal of the American Chemical Society since January 2022. Besides his scientific activities, CCH enjoys literature, history, cooking and wine tasting, probably a reminiscence of his childhood spent in the vineyards in Fleurie (La Reine), one of the famous crûs of Beaujolais, just ca. 50 km north of Lyon. This article has not yet been cited by other publications.

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简介：弥合差距：从跨界催化中学习

这篇文章是其中的一部分弥合差距：从跨界催化中学习专刊。催化是一门核心科学，它将对开发更可持续的过程做出关键贡献，这与当前与气候变化和环境问题相关的新出现但紧迫的社会挑战有关。传统上，催化被细分为三个领域：多相催化、均相催化和生物催化，并且在这三个领域内还可以根据热催化、电催化和光催化过程进行分类。这些学科大多是独立发展的，以应对特定的科学和不同的催化挑战。由于催化是一种分子现象，其中键在催化活性位点上断裂并形成，因此毫无疑问局部结构的重要性。然而，多年来人们已经认识到，动力学和长程相互作用对于催化剂设计和合理化所有类型催化剂的整体催化性能通常同样重要。近年来，这些不同领域之间的交叉融合和催化剂设计的互补混合方法已经开始解决传统领域的一些固有局限性。这些努力使这些学科的一些最有吸引力的特征得以结合。作为 NCCR Catalysis 的两名成员，这是一项旨在开发更可持续的催化过程的瑞士范围内的努力，我们一直特别感兴趣的是汇集 21 篇评论文章，这些文章总结了本领域的最新催化技术的专题问题化学评论创造了“弥合差距：从跨界催化中学习”。光子、电子和质子的暂时传递或移除是光合作用的标志。尽管大自然在进化过程中已经掌握了这种高度交叉调节的过程，但模拟这种复杂的光催化过程仍然极具挑战性，无论是均相还是异相催化剂。本着仿生精神，在密闭环境中对催化成分进行区室化，可以实现高度的空间组织，并能及时、定向地输送或去除试剂和产品。在他们的评论中，Pullen、Reek 和同事总结了超分子配位笼内人工光合作用和光催化领域的最新技术。最小化相互抑制的另一种方法——通常在反应级联中观察到——依赖于将不相容的催化伙伴区室化。两篇评论提供了关于旨在结合均相和多相催化剂和生物催化剂以合成高附加值产品的策略的互补观点：Gröger、Lipschutz 和 Gallou 以及 Lavandera、Gotor-Fernández 和同事。为了最大限度地减少多步合成过程中的分离和纯化步骤，并发催化级联引起了越来越多的关注。由于酶已经进化到可以在复杂的细胞介质中运行，因此它们擅长催化此类复杂任务。然而，他们的反应曲目是相当有限的。为了克服这个限制，已经致力于将均相催化剂与酶结合用于化学酶并发级联反应。然而，这已被证明具有挑战性，因为酶和均相催化剂经常会相互抑制。为了避免这个问题，已经采用了各种划分策略来实现并发级联。这些包括顺序催化——作为“时间分隔”的一种形式——双相介质、MOF、沸石、多相催化剂、PDMS-套管和膜、藻酸盐珠以及非离子表面活性剂等。对于非专业读者来说重要的是，作者提供清晰地讨论了这些划分策略的挑战和局限性。为了补充传统的酶固定化和区室化策略，金属有机框架 (MOF) 作为用于封装酶的多功能且高度组织化的主体而引起了越来越多的关注。Shi、Zhou 及其同事对 (i) 酶和 MOF 之间的协同相互作用以及 (ii) 仿生 MOF 的组装和催化潜力提出了深刻的见解。电催化引入了另一层复杂性，它需要 NADPH 和 ATP 的分隔和回收，以最大限度地降低能量成本。为了维持生命所必需的非平衡反应网络的复杂网络，新陈代谢依赖 ATP 和 NAD(P)H 作为能量货币。本着循环经济的精神，使用 ATP 和 NAD(P) Zhou 及其同事对 (i) 酶和 MOF 之间的协同相互作用以及 (ii) 仿生 MOF 的组装和催化潜力提出了深刻的见解。电催化引入了另一层复杂性，它需要 NADPH 和 ATP 的分隔和回收，以最大限度地降低能量成本。为了维持生命所必需的非平衡反应网络的复杂网络，新陈代谢依赖 ATP 和 NAD(P)H 作为能量货币。本着循环经济的精神，使用 ATP 和 NAD(P) Zhou 及其同事对 (i) 酶和 MOF 之间的协同相互作用以及 (ii) 仿生 MOF 的组装和催化潜力提出了深刻的见解。电催化引入了另一层复杂性，它需要 NADPH 和 ATP 的分隔和回收，以最大限度地降低能量成本。为了维持生命所必需的非平衡反应网络的复杂网络，新陈代谢依赖 ATP 和 NAD(P)H 作为能量货币。本着循环经济的精神，使用 ATP 和 NAD(P) 为了维持生命所必需的非平衡反应网络的复杂网络，新陈代谢依赖 ATP 和 NAD(P)H 作为能量货币。本着循环经济的精神，使用 ATP 和 NAD(P) 为了维持生命所必需的非平衡反应网络的复杂网络，新陈代谢依赖 ATP 和 NAD(P)H 作为能量货币。本着循环经济的精神，使用 ATP 和 NAD(P)⁺在细胞内不断循环。在他们的评论中，Armstrong、Megarity 和同事总结了他们在创造电化学叶 (e-Leaf) 的受限电催化环境中重现此类生命特征的努力。将蛋白质膜电化学扩展到铁氧还蛋白-NADP ^{+对 NAD(P)H 的可逆电化学再生}固定在纳米结构氧化铟锡薄膜孔隙中的还原酶 (FNR) 使酶级联电催化成为可能。为了回收用过的 ATP，他们依赖于同样固定在 ITO 纳米孔中的激酶对。作者讨论了已在 e-Leaf 中实施的各种酶级联网络。该领域的一个里程碑是四酶线性级联。FNR、苹果酸酶、延胡索酸酶和l-天冬氨酸氨裂解酶的纳米限制使丙酮酸和 CO ₂电化学转化为天冬氨酸，并结合固定 CO ₂所需的 NADPH 的再生丙酮酸。在仿生精神中，电催化能够在两个方向上驱动这种酶促级联，具体取决于施加的电势。这项工作总结了在设计多功能电催化平台以组装复杂酶级联和研究让人联想到新陈代谢的复杂催化网络方面的开创性工作。为了将生物催化的范围扩大到涉及光生激发态中间体的反应，光生物催化在过去 25 年中引起了越来越多的关注。在整个审查过程中，Hyster 和同事确定并深入了解了迄今为止已报道的四种光生物催化系统：(i) 光酶催化，(ii) 协同光酶催化，(iii) 串联光催化-酶反应，(iv) 与自然光合作用相结合的酶促反应。总结了新近可及的反应的机理考虑和巨大的合成潜力，以突出该领域尚未开发的机会。一个活细胞，包括它的各种细胞器，可以被视为最终的分子工厂，能够协调精确的交叉调节反应网络。1973 年，Cohen 和 Bailey 开创了重组 DNA 技术。这一里程碑开启了将细胞转化为分子工厂以过量生产高附加值化学品（胰岛素、青蒿酸等）或生物燃料的迷人前景。Zhao 及其同事的评论总结了代谢工程领域的最新技术。作者批判性地分析了广泛应用的策略，以最大限度地提高工程宿主生物体中目标化合物的产量：设计、构建、测试和学习。该领域在过去 30 年取得了显着增长，这得益于各个领域的突破，包括：PCR 技术、定向进化、CRISPR-cas9、蛋白质组学、代谢组学、机器学习等。虽然葡萄糖通常作为碳源，但它高度希望依靠更便宜的替代品。相应地，最近的努力努力依靠：塑料解构、甲醇、CO、CO 代谢组学、机器学习等。虽然葡萄糖通常用作碳源，但非常希望依赖更便宜的替代品。相应地，最近的努力努力依靠：塑料解构、甲醇、CO、CO 代谢组学、机器学习等。虽然葡萄糖通常用作碳源，但非常希望依赖更便宜的替代品。相应地，最近的努力努力依靠：塑料解构、甲醇、CO、CO_2个等。作者提供了令人信服的论据，即代谢工程提供了一种可持续的替代传统石油生产工艺的方法。主要的技术瓶颈似乎是缺乏大规模生产的设施。使用细胞作为分子工厂来生产感兴趣的化合物（表型）的主要特征之一是表型-基因型连锁，从而能够直接识别改进的酶突变体（基因型）。要充分利用自动化 DNA 合成和下一代测序领域令人瞩目的发展，就需要超高通量筛选工具。在他们的权威评论中，Hollfelder 和同事总结了液滴微流体的最新技术，结合 NGS 和深度学习算法优化生物催化剂。⁷变体。最近的发展包括使用无标记检测方法，包括质谱法。2020 年是 Staudinger 首次发表聚合物论文一百周年。在过去的一个世纪里，人造聚合物的使用量不断增长，预计到 2030 年将达到每年 7 亿吨。令人担忧的是，这些聚合物中有 80% 最终被填埋，只有不到 20% 被回收利用。本着循环经济的精神，聚合物代表了一种尚未开发的积木来源。在他们的彻底审查中，Taton、Marty、André 和同事总结了塑料回收和升级回收生物催化解决方案领域的最新技术。他们提供了令人信服的论据，证明 PET 和 PLA 的酶促降解已达到高度成熟，而所有碳聚合物仍然难以通过酶促解构。CO的催化还原₂要求及时运送多种试剂。掌握这种极具挑战性的反应是减少碳足迹的关键。目前正在开发几种互补的催化策略以实现 CO ₂固定，并在本专题中进行了总结。尽管它可能是地球上最古老的碳源，但依靠 CO ₂作为（唯一）碳源，目前代表着合成生物学的圣杯。在他们的评论中，Winkler、Tinzl、Glueck 和同事全面概述了（脱）羧化酶及其在生物技术应用中的潜力。在介绍了与羧化反应相关的热力学挑战以及用于推动反应形成 C-C 键的策略之后，作者介绍了所有已知的天然存在的（脱）羧化酶、它们相关的（人工）途径，以及与每个 CO ₂固定步骤相关的能量成本（即 ATP、NAD(P)H 等）。评论最后讨论了工程更高效（人造）CO _2的前景-修复途径及其潜在的社会经济后果。改进化学酶促羧化级联反应的策略之一可能是设计高效的人工CO _{2 -}固定酶。在这种情况下，费托多相催化过程能够将一氧化碳和氢气转化为液态烃。由于一氧化碳与二氮是等电子的，因此在固氮酶相关机理研究的背景下，它已被广泛用作底物替代物。引人注目的是，Ribbe、Hu 及其同事在 2010 年报道了来自Azobacter vinilandii的含钒固氮酶催化 CO 甚至 CO _2的转化做空碳氢化合物。_{这一发现为将 CO 或 CO 2}以碳中性方式转化为碳氢化合物开辟了迷人的前景。固氮酶的各个亚基、分离的辅因子以及合成的辅因子模拟物──包括 [(RS) ₄ Fe ₄ S ₄ ]──产生更大的产物分布并催化 CO、CO ₂和 CN还原^为C ₁ –C ₇碳氢化合物。与需要能量的费托过程形成鲜明对比的是，这些酶促反应或 (RS) ₄ Fe ₄ S ₄催化反应在环境条件下进行并利用 H ⁺和牺牲电子^-捐助者。这些发现不仅对生物技术应用很有趣，而且可能与碳固定的原始过程具有进化相关性。Fischer-Tropsch (FT) 过程确实是一个典型的例子，说明了多相催化的美丽和复杂性，其中 C-O 键被破坏，C-C 键形成以在通常为 CO 的氢化过程中生成更高级的碳氢化合物或醇。 Saeys 及其同事总结了该领域的最新技术，重点关注表面科学、微观动力学和计算模型如何提供对 FT 催化剂中反应状态和反应机制的分子水平理解。如上所述，与分子催化剂甚至酶相比，这些系统很难在分子水平上描述，包括备受争议和未知的活性位点。这些经常产生就地来自反应物和已经很复杂的物体，例如 FT 中使用的支撑纳米粒子。这推动了该领域向多个方向发展，包括自下而上到自上而下的合成方法、构建模型系统和开发先进的光谱技术。在解决基于金属纳米粒子的更具选择性和稳定性的催化剂的开发时，一种方法是考虑引入额外的元素；合金的形成通过避免形成大的整体和/或通过改变纳米粒子或反应性金属位点的电子性质来改变表面位点的性质。Furukawa 及其同事成功地批判性地分析了金属合金领域；按照金属合金和各种术语的分类，_X和电催化过程。为了理解这些复杂的物体，郑和同事在他们的评论中讨论了原子分散的金属催化剂和配体保护的原子精确金属簇如何有助于建模和更好地理解非均相催化剂，从而允许描述金属-支撑界面上的局部协调和配体如何影响金属位点的反应性。另一方面，Gross 和同事回顾了高空间分辨率显微镜和光谱学如何提供关于配体和表​​面相互作用的分子水平洞察力，直至单个粒子。虽然是大物体，但沸石通常被认为是理想的多相催化剂，其中氧化物晶格的结晶性质提供了生成明确定义的金属位点的方法，结合了这些材料的微晶结构。此外，它们提供明确定义的空腔（与上述讨论产生共鸣的隔间）不仅可以容纳活性位点，还可以容纳大物体，例如团簇和纳米粒子。在此背景下，Yu 和同事详细讨论了沸石，从活性位点的分类和动力学到合成和表征方法，以及它们在众多过程中的应用。此外，Chizallet 及其同事展示了沸石如何通过结合先进的光谱和计算方法详细了解其活性位点结构和微孔环境，处于多相催化和分子催化的十字路口。弥合微孔世界和分子世界之间的差距，Dincǎ 及其同事研究了相应的金属有机框架 (MOF)，揭示了这些具有分子定义框架的独特固态结构的资产。同样，孤立位点也可以在扩展表面上找到，例如氮掺杂碳。这些材料允许承载高度分散的金属位点，通常称为单原子催化剂。这些材料可以被视为理想的系统，能够弥合均相和多相催化之间的差距，而且由于这些载体的导电性质，还可以在基本水平上理解催化中的氧化还原过程。在他们的评论中，Bates、Stahl 及其同事在有氧氧化反应和氧还原电催化之间进行了独特的比较，进一步说明如何将概念从电催化转移到热催化。作为补充，Patzke 和同事讨论了如何现场/操作表征技术能够监测析氧 (OER) 和还原 (ORR) 反应中涉及的多电子过程的催化剂。该审查还强调了在相关条件下的监测如何能够制定战略来审视重组过程，例如。最后，为了说明催化中的一些重要挑战，Hutchings 及其同事回顾了化学的圣杯之一，并讨论了用于甲烷选择性氧化的催化剂开发。该领域突出了每个领域的具体挑战，并说明了三类催化剂之间的交叉融合如何有助于设计更好的催化剂。我们希望您会喜欢阅读这本评论文章集以及即将出版的与跨界催化相关的文章。托马斯·R。Ward 从 ETHZ 获得博士学位，与教授一起工作。C 上的 Venanzi 和 Seebach_3个-对称配体及其在均相催化中的应用。随后，他加入了康奈尔大学的 Roald Hoffmann 教授攻读博士后。他们与福特汽车公司合作，模拟并合理化了氧化物负载贵金属在三元催化剂中还原 NO 的多功能性。回到瑞士后，他专注于人工金属酶的开发。这种混合催化剂弥合了均相催化和酶催化之间的差距。自 2008 年以来，他一直担任巴塞尔大学的全职教授，并与瑞士国家催化能力中心合作，旨在将瑞士建设成为国际公认的可持续化学研究、教育和创新中心。Christophe Copéret (CCH) 在美国普渡大学获得博士学位，师从 E. i. 教授。根岸, 他在那里研究了通过 Pd 催化的羰基化反应合成复杂分子。在 KB Sharpless 教授（斯克里普斯研究所）完成博士后研究后，CCH 于 1998 年获得 CNRS 的研究职位，并于 2008 年晋升为 CNRS 研究主任。自 2010 年以来，CCH 一直担任化学与应用系教授生物科学，苏黎世联邦理工学院。他的科学兴趣在于分子、材料和表面化学以及 NMR 光谱学的前沿领域，旨在通过详细的机理研究和结构-活性关系设计分子定义的固体催化剂。CCH 目前正在与 R. Buosanti 教授（EPFL）协调瑞士国家催化能力中心与工具相关的工作，他一直是美国化学学会杂志自 2022 年 1 月起。除了他的科学活动外，CCH 还喜欢文学、历史、烹饪和品酒，这可能是他在弗勒里 (La Reine) 的葡萄园度过的童年回忆，弗勒里 (La Reine) 是博若莱著名的 crûs 之一, 只是约 里昂以北 50 公里。这篇文章尚未被其他出版物引用。