The Reduction of Carbon Dioxide by Enzymes Adsorbed on Electrodes: from Mechanistic Studies to Bioinspired Catalysts

通过电极上吸附的酶还原二氧化碳：从机理研究到仿生催化剂

• 批准号: BB/J000124/1
• 负责人: Erwin Reisner
• 金额: $ 39.52万
• 依托单位: University of Cambridge
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2012
• 资助国家: 英国
• 起止时间: 2012 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=BB%2FJ000124%2F1
• 关键词: Reduction; Carbon; Dioxide; Enzymes; Adsorbed

Carbon dioxide (CO2) is produced by the combustion of carbon-containing molecules, such as fossil fuels, to power industry, for transportation, and in our homes. Burning fossil fuels is not only causing the level of CO2 in the atmosphere to increase (CO2 is a greenhouse gas and a major contributor to global warming) it is also depleting valuable resources that are required for the manufacture of plastics, chemicals, fertilizers - and countless other requirements of modern society. Unfortunately, CO2 is a very stable and unreactive molecule, and the only large scale process known that can remove CO2 from the atmosphere and use it to regenerate a carbon-containing fuel is biological photosynthesis (growing plants and trees). Therefore, an industrial process that could use the energy from sunlight, or a green-electricity source, to take CO2 out of the atmosphere and turn it into a useful fuel or chemical would revolutionise modern society, by supplying both our energy and material demands. Of course, no such process currently exists. The aim of this proposal is to explore a new approach for the development of such a process. Some bacteria use enzymes called formate dehydrogenases (FDHs) to catalyse the oxidation (= burning) of formate to CO2, and extract energy from this reaction in order to survive. Chemically, formate is one of the simplest hydrocarbons - it is already used as a chemical building block (feedstock) in industry, and formate 'fuel cells' are being developed. Turning a formate dehydrogenases 'in reverse' would turn CO2 into formate, a useful product. In fact, a small number of specialised bacteria use special 'tungsten-containing' FDHs to catalyse this reverse reaction - and live off the tiny amount of energy that they extract. In a pilot study we showed that the tungsten FDH from a bacterium called Syntrophobacter fumaroxidans can act as an extremely efficient electrically-driven catalyst for the reduction of CO2 to formate. In this project we aim to find out 'how the tungsten formate dehydrogenase does it'. We will start by looking for and characterising tungsten FDHs from different organisms, to find those that are the best for our experiments. Then we will apply sophisticated biochemical, electrochemical and physical techniques to aim to find out how they work - and why they work so well. Finally, we will compare our biological catalysts with available synthetic catalysts, aiming to find out how to improve the synthetic catalysts, and to develop 'demonstration devices' that show how efficient CO2 reduction catalysts can be powered by solar radiation and used in fuel cells.

二氧化碳（CO2）是由含碳分子（如化石燃料）燃烧产生的，用于工业、运输和我们的家庭。燃烧化石燃料不仅导致大气中二氧化碳含量增加（二氧化碳是一种温室气体，是全球变暖的主要原因），而且还消耗了制造塑料、化学品、化肥以及现代社会无数其他需求所需的宝贵资源。不幸的是，二氧化碳是一种非常稳定和不活泼的分子，唯一已知的可以从大气中去除二氧化碳并利用它来再生含碳燃料的大规模过程是生物光合作用（种植植物和树木）。因此，利用太阳能或绿色能源将大气中的二氧化碳转化为有用的燃料或化学品的工业过程将彻底改变现代社会，满足我们对能源和物质的需求。当然，目前还不存在这样的流程。这项建议的目的是探讨发展这一进程的新办法。一些细菌利用一种叫做甲酸脱氢酶（FDHs）的酶来催化甲酸氧化（燃烧）成二氧化碳，并从这个反应中提取能量以维持生存。从化学上讲，甲酸盐是最简单的碳氢化合物之一，它已经被用作工业上的化学组成部分（原料），甲酸盐“燃料电池”正在开发中。将甲酸脱氢酶“反向”转化将把二氧化碳转化为甲酸盐，这是一种有用的产物。事实上，少数特殊的细菌使用特殊的“含钨”FDHs来催化这种逆反应，并依靠它们提取的少量能量生存。在一项初步研究中，我们发现从一种叫做富马氧化合滋养菌的细菌中提取的钨FDH可以作为一种非常有效的电驱动催化剂，将二氧化碳还原为甲酸盐。在这个项目中，我们的目标是找出甲酸钨脱氢酶是如何做到这一点的。我们将从寻找和描述来自不同生物的钨FDHs开始，以找到最适合我们实验的那些。然后，我们将运用复杂的生化、电化学和物理技术，旨在找出它们是如何工作的，以及它们为什么工作得这么好。最后，我们将把我们的生物催化剂与现有的合成催化剂进行比较，旨在找出如何改进合成催化剂，并开发“示范装置”，展示如何利用太阳辐射为二氧化碳还原催化剂提供动力，并将其用于燃料电池。

项目成果

Oxidation-State-Dependent Binding Properties of the Active Site in a Mo-Containing Formate Dehydrogenase.

• DOI: 10.1021/jacs.7b03958
• 发表时间: 2017-07-26
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Robinson WE;Bassegoda A;Reisner E;Hirst J
• 通讯作者: Hirst J

High Performance Reduction of H2O2 with an Electron Transport Decaheme Cytochrome on a Porous ITO Electrode

在多孔 ITO 电极上使用电子传输十血红素细胞色素高性能还原 H2O2

• DOI: 10.17863/cam.8140
• 发表时间: 2017
• 作者: Reisner E

Reversible and Selective Interconversion of Hydrogen and Carbon Dioxide into Formate by a Semiartificial Formate Hydrogenlyase Mimic.

通过半人工甲酸氢解酶模拟物将氢气和二氧化碳可逆且选择性地相互转化为甲酸。

• DOI: 10.1021/jacs.9b09575
• 发表时间: 2019
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Sokol KP

Carbon Dots as Versatile Photosensitizers for Solar-Driven Catalysis with Redox Enzymes

碳点作为多功能光敏剂用于氧化还原酶太阳能驱动催化

• DOI: 10.17863/cam.7975
• 发表时间: 2016
• 作者: Hutton G

Understanding how the rate of C-H bond cleavage affects formate oxidation catalysis by a Mo-dependent formate dehydrogenase

了解 C-H 键断裂速率如何影响 Mo 依赖性甲酸脱氢酶的甲酸氧化催化

• DOI: 10.17863/cam.54200
• 发表时间: 2020
• 作者: Robinson W