Using nature's blueprint to expand catalysis with Earth-abundant metals.
Using nature's blueprint to expand catalysis with Earth-abundant metals.
复制标题
DOI：
10.1126/science.abc3183
复制
发表时间：
2020-08-14
期刊：
影响因子：
--
通讯作者：
Surendranath Y
中科院分区：
文献类型：
--
作者：
Bullock RM;Chen JG;Gagliardi L;Chirik PJ;Farha OK;Hendon CH;Jones CW;Keith JA;Klosin J;Minteer SD;Morris RH;Radosevich AT;Rauchfuss TB;Strotman NA;Vojvodic A;Ward TR;Yang JY;Surendranath Y
许多对生命至关重要的氧化还原转化都是由以地球丰富的金属为特征的金属酶催化的。相比之下，铂族金属几十年来一直是许多工业催化反应的基石，提供高活性，热稳定性和对化学毒物的耐受性。我们断言，大自然的蓝图提供了广泛扩大使用丰富的金属催化的基本原则。我们强调了丰富的金属的关键物理特性，使其与贵金属区分开来，我们期待大自然了解如何利用丰富的金属的固有属性来生产高效的催化剂，用于对燃料和化学品的可持续生产和转化至关重要的反应。催化对社会产生了变革性的影响，在现代材料、药物、燃料和化学品的生产中发挥着至关重要的作用。几十年来，贵金属一直是许多工业催化过程的基石，提供高活性，稳定性和对毒物的耐受性。与此形成鲜明对比的是，对生命至关重要的氧化还原催化是由金属酶进行的，金属酶的特征是地球上丰富的金属（EAM）。某些稀土金属在陆地上的丰度是贵金属的104倍，因此，增加使用稀土金属将降低成本和环境足迹。除了这些实际的考虑，EAM显示不同的反应性，源于其特征的电子结构，热化学和动力学。EAM的行为为催化剂设计提供了令人信服的科学机会。我们断言，大自然的蓝图提供了基本原则，大大扩大使用的EAM在可持续催化。精细调节EAM活性位点周围的局部环境是使其能够用于催化的关键。这种控制是通过氨基酸环境的定向进化在酶催化中实现的，从而产生具有非凡催化性能的工程化酶。类似地，在分子催化中，改性配体的空间和电子性质可以导致一些EAM催化剂具有比从贵金属催化剂获得的性能更优越的性能上级。此外，对于非均相催化剂，活性位点的局部环境和电子结构可以通过与其他金属或主族元素键合来改变，从而促进与涉及贵金属的反应途径不同的反应途径。EAM催化剂设计的创新表明，它们有潜力催化许多传统上依赖贵金属的反应，尽管在活性、选择性、寿命或能源效率方面还需要进一步改进。EAM的特点指出了一个总体需要改进的理论和计算方法，准确地对待他们的多组态电子结构。酶仅使用EAM在温和条件下催化多种反应的显着能力凸显了发现新催化作用的令人信服的机会。虽然酶是利用EAM特性的通用平台，但它们在一些工业催化过程所需的苛刻pH、温度、压力和溶剂条件下不够稳健。因此，定向进化需要系统的策略来延长工程酶的反应性和持久性。对于分子催化剂，配体的可调谐性提供了系统地改变EAM活性的机会。关键的挑战包括增强金属-配体协同性，控制向EAM活性位点的运输，以及掌握EAM中心与金属基和有机基氧化还原活性配体的相互作用。在多相催化中，调整EAM的晶格环境为催化剂的发现提供了新的机会，但对于实际应用，EAM催化剂应表现出长期稳定性和高活性中心密度。因此，需要在合成具有可调相和纳米结构的材料方面取得进展，以及深入了解EAM催化剂如何在持续的催化周转下发生电子和结构变化。控制EAM反应模式的策略，加上合成方法和光谱和计算技术的进步，是系统地使用EAM在可持续催化的关键。地球上丰富的金属的催化作用。大自然的蓝图提供了基本原则，通过控制局部环境和金属中心的电子结构来扩大丰富的金属在催化中的应用。实例包括用于N2还原的基于固氮酶的酶催化剂、用于氧和二氧化碳还原的基于金属卟啉的分子催化剂、以及用于加氢脱硫和析氢反应的多相催化中的金属硫属化物。
Numerous redox transformations that are essential to life are catalyzed by metalloenzymes that feature Earth-abundant metals. In contrast, platinum-group metals have been the cornerstone of many industrial catalytic reactions for decades, providing high activity, thermal stability, and tolerance to chemical poisons. We assert that nature’s blueprint provides the fundamental principles for vastly expanding the use of abundant metals in catalysis. We highlight the key physical properties of abundant metals that distinguish them from precious metals, and we look to nature to understand how the inherent attributes of abundant metals can be embraced to produce highly efficient catalysts for reactions crucial to the sustainable production and transformation of fuels and chemicals. Catalysis has had a transformative impact on society, playing a crucial role in the production of modern materials, medicines, fuels, and chemicals. Precious metals have been the cornerstone of many industrial catalytic processes for decades, providing high activity, stability, and tolerance to poisons. In stark contrast, redox catalysis essential to life is carried out by metalloenzymes that feature exclusively Earth-abundant metals (EAMs). The terrestrial abundance of some EAMs is 104 times that of precious metals, and thus their increased use would lead to reduced cost and environmental footprint. In addition to these practical considerations, EAMs display distinct reactivity profiles that originate from their characteristic electronic structure, thermochemistry, and kinetics. The behavior of EAMs provides compelling scientific opportunities for catalyst design. We assert that nature’s blueprint provides essential principles for vastly expanding the use of EAMs in sustainable catalysis. Exquisite tuning of the local environment around EAM active sites is key to enabling their use in catalysis. Such control is achieved in enzymatic catalysis by directed evolution of the amino acid environment, resulting in engineered enzymes with extraordinary catalytic performance. Similarly in molecular catalysis, modifying the steric and electronic properties of ligands can lead to some EAM catalysts with performance superior to that obtained from precious metal catalysts. In addition, for heterogeneous catalysts, the local environment and electronic structure of active sites can be modified by bonding to other metals or main-group elements, facilitating reaction pathways distinct from those involving precious metals. Innovations in the design of EAM catalysts demonstrate their potential to catalyze many of the reactions that traditionally relied on precious metals, although further improvements are needed in activity, selectivity, lifetime, or energy efficiency. The characteristics of EAMs point to an overarching need for improved theories and computational methods that accurately treat their multiconfigurational electronic structure. The remarkable ability of enzymes to catalyze a variety of reactions under mild conditions, using only EAMs, highlights compelling opportunities for the discovery of new catalysis. Although enzymes are versatile platforms for harnessing the properties of EAMs, they are insufficiently robust under the harsh pH, temperature, pressure, and solvent conditions required for some industrial catalytic processes. Thus, systematic strategies are needed for directed evolution to extend the reactivity and persistence of engineered enzymes. For molecular catalysts, the tunability of the ligands provides opportunities for systematically varying the activities of EAMs. Key challenges include enhancing metal-ligand cooperativity, controlling transport to EAM active sites, and mastering the interactions of EAM centers with both metal-based and organic-based redox-active ligands. In heterogeneous catalysis, tuning the lattice environment of EAMs offers new opportunities for catalyst discovery, but for practical applications EAM catalysts should exhibit long-term stability and high active-site density. Thus, advances are needed in the synthesis of materials with tunable phase and nanostructure, as well as insights into how EAM catalysts undergo electronic and structural changes under sustained catalytic turnover. Strategies for controlling EAM reactivity patterns, coupled with advances in synthetic methods and spectroscopic and computational techniques, are critical for the systematic use of EAMs in sustainable catalysis. Catalysis by Earth-abundant metals. Nature’s blueprint provides the fundamental principles for expanding the use of abundant metals in catalysis by controlling the local environment and electronic structure of metal centers. Examples include nitrogenase-based enzymatic catalysts for N2 reduction, metalloporphyrin-based molecular catalysts for reduction of oxygen and carbon dioxide, and metal chalcogenides in heterogeneous catalysis for hydrodesulfurization and hydrogen evolution reactions.
登录
查看更多内容
影响因子：
15
作者：
Baek, Jayeon;Rungtaweevoranit, Bunyarat;Yaghi, Omar M.
通讯作者：
Yaghi, Omar M.
影响因子：
56.9
作者：
Carsch, Kurtis M.;DiMucci, Ida M.;Betley, Theodore A.
通讯作者：
Betley, Theodore A.
影响因子：
7.7
作者：
Brandenberg OF;Fasan R;Arnold FH
通讯作者：
Arnold FH
用氧化还原活性双（Imino）吡啶铁配合物氧化添加碳碳键。
影响因子：
15
作者：
Darmon JM;Stieber SC;Sylvester KT;Fernández I;Lobkovsky E;Semproni SP;Bill E;Wieghardt K;DeBeer S;Chirik PJ
通讯作者：
Chirik PJ
影响因子：
15
作者：
Dey, Subal;Rana, Atanu;Dey, Abhishek
通讯作者：
Dey, Abhishek