SusChEM: Electrocatalysis with Butterfly [2Fe-2S] Clusters

氢是最简单的分子，今天是一个价值数十亿美元的工业，它主要提供氢气与氮气结合来生产氨肥，这是为世界人口生产足够的粮食所需的肥料，用于从化石燃料中去除硫，以及用于生产现代社会所需的材料的工业应用。此外，当今世界面临的重大挑战之一是需要可持续、清洁和具有成本效益的能源和燃料。氢是一种高能燃料，在燃烧时(或在燃料电池中)只是将水作为废气产物。不幸的是，今天生产的96%的氢气是从极高温度和高压的蒸汽对碳氢化合物的昂贵作用中获得的，这一过程既浪费能源又浪费原材料。分析表明，世界上2%的能源被用于这些过程，如果没有使用氢气生产用于粮食生产的肥料的过程，世界上一半的人口不会有今天的生命。这项由化学部催化计划资助的研究项目正在探索利用电力直接从水中生产氢气的高效、清洁和可持续的过程。为了在低温和压力下从水中生产氢气，需要一种廉价、容易获得的催化剂。亚利桑那大学的Dennis L.Lichtenberger教授、Jeffrey Pyun教授和Richard S.Glass教授以及普渡大学的Dennis H.Evans教授正在研究利用电力和由廉价且充足的铁和硫磺组成的催化剂从水中产生氢气的方法。这项研究中的催化剂的灵感来自厌氧细菌中发现的一种酶，该酶从[2Fe-2S]簇位产生氢气，该簇位具有表示为蝴蝶的结构。打字。虽然这种酶产生氢的速度非常快，但在这个项目中制备的有机金属蝴蝶[2Fe-2S]团簇的速度要快几个数量级。在这个项目中观察到的高产氢率表明，与生物酶和其他无机催化剂相比，不同的因素在发挥作用。本项目正在探索合成新的有机金属[2Fe-2S]簇合物催化剂，并研究(1)实现如此快速电催化制氢的机理，(2)将[2Fe-2S]簇合物引入金属聚合物以提高催化剂的水溶性和耐用性，以及(3)实现反应催化剂在空气中的高稳定性的方法。该项目结合了合成金属有机化学、聚合物化学、电化学和计算化学方面的专业知识，旨在了解从水中高效电催化生产分子氢所需的基础知识，并教育学生应对未来复杂的科学挑战所需的多学科和团队方法。

SusChEM: Electrocatalysis with Butterfly [2Fe-2S] ClustersThe production of hydrogen, the simplest molecule, is a multi-billion dollar industry today that provides hydrogen primarily for combination with nitrogen to produce ammonia fertilizer needed to grow sufficient food for the world population, for removal of sulfur from fossil fuels, and for industrial applications needed to produce the materials for a modern society. Furthermore, one of the grand challenges facing the world today is the need for sustainable, clean, and cost-effective sources of energy and fuels. Hydrogen is a high energy fuel that on burning (or in fuel cells) simply has water as the exhaust product. Unfortunately 96% of the hydrogen produced today is obtained from the expensive action of extremely high temperature and pressure steam on hydrocarbons, a process that is wasteful of both energy and raw materials. Analysis shows that 2% of the world energy is used in these processes and half the world population would not be alive today without the process that uses hydrogen to produce fertilizer for food production. This research project, funded by the Catalysis Program of the Chemistry Division, is exploring the use of electricity to produce hydrogen directly from water in an efficient, clean and sustainable process. To effect the production of hydrogen from water at low temperature and pressure, an inexpensive, readily available catalyst is required. Professors Dennis L. Lichtenberger, Jeffrey Pyun and Richard S. Glass of the University of Arizona and Professor Dennis H. Evans of Purdue University are investigating the production of hydrogen from water using electricity and catalysts composed of inexpensive and plentiful iron and sulfur.The catalysts in this study are inspired by an enzyme found in anaerobic bacteria that produces hydrogen from a [2Fe-2S] cluster site that has a structure denoted as a ?butterfly? type. Although the enzyme generates hydrogen very rapidly, the organometallic butterfly [2Fe-2S] clusters prepared in this project are orders of magnitude faster. The high rates of hydrogen production observed in this project indicate different factors are at play compared to both the biological enzyme and to other inorganic catalysts. This project is exploring the synthesis of new organometallic [2Fe-2S] cluster catalysts and investigating (1) the mechanism that allows for such fast electrocatalytic hydrogen production, (2) the incorporation of the [2Fe-2S] clusters into metallopolymers for increased water solubility and durability of the catalysts, and (3) approaches to achieve high stability of the reactive catalysts in air. The project combines expertise in synthetic organometallic chemistry, polymer chemistry, electrochemistry, and computational chemistry directed toward the fundamental understanding needed to devise efficient electrocatalytic production of molecular hydrogen from water, and educates students in the multidisciplinary and team approaches needed to address complex scientific challenges in the future.