SusChEM: Rational design of aqueous interfaces of Earth abundant and nontoxic transition metal sulfides for photocatalytic conversion of CO2 to fuels

SusChEM：地球丰富且无毒的过渡金属硫化物的水界面的合理设计，用于二氧化碳光催化转化为燃料

• 批准号: 1336845
• 负责人: Ponisseril Somasundaran
• 金额: $ 45.71万
• 依托单位: Columbia University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-08-01 至 2018-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1336845&HistoricalAwards=false
• 关键词: SusChEM; Rational; design; aqueous; interfaces

PI: Somasundaran, PonisserilProposal Number: 1336845Institution: Columbia UniversityTitle: SusChEM: Rational design of aqueous interfaces of Earth abundant and nontoxic transition metal sulfides for photocatalytic conversion of CO2 to fuelsThis project focuses on understanding aqueous interfaces of Earth abundant and nontoxic transition metal sulfides to engineer a cost-effective photo-electrocatalytic CO2 reduction system. The biggest roadblock to making scalable the sun-light powered synthesis of carbonaceous fuels from CO2 and water is the lack of a catalysts which is simultaneously efficient, cheap, and environmentally benign. The development of such a catalyst is hindered by the infancy of the mechanistic understanding of the proton-coupled multiple electron transfers involved into the CO2 reduction beyond CO and formate. The proposed interdisciplinary research will bridge this knowledge gap by systematically studying for the first time copper and iron sulfide minerals as novel and cheap photocatalytic materials. A novel molecular cocatalytic approach is suggested to overcome the thermodynamic and kinetic limitations of CO2 reduction towards energy-dense fuels. The objective is to determine the mechanisms of the reaction dependence on molecular cocatalysts at the interfaces and in bulk electrolyte, with the ultimate goal to develop more sustainable and efficient photosynthetic systems. Towards this ambitious goal, a team from Columbia University will study for the first time the multiscale physics and chemistry driving artificial photosynthesis of carbonaceous fuels by iron and copper sulfides, using advanced operando FTIR and Raman spectro-electrochemical, (photo)electrochemical, and theoretical (e.g., Density Fuction Theory) methods. The new more efficient photosynthetic systems based on copper and iron sulfides developed during the research will be a practical step towards scaling up renewable energy. It will lead to novel scalable strategies for the rational design of the interfaces of metal sulfides with water. Apart from artificial photosynthesis, this outcome can find application in immobilizing radionuclides in environmental remediation, as well as in mineral processing (selective separation) of sulfide minerals, in the design of greener chemicals. In addition, this knowledge will broaden our understanding of biogeochemical process including processes in acid-mine drainage, cycling of iron and cupper in deep oceans, and eventually the origin of life. The general results of the research and the new methodology will be included in the PI's undergraduate/graduate level courses.

PI：Somasundaran，Ponisseril 提案编号：1336845 机构：哥伦比亚大学 标题：SusChEM：合理设计地球丰富且无毒的过渡金属硫化物的水界面，用于将二氧化碳光催化转化为燃料 该项目重点了解地球丰富且无毒的过渡金属硫化物的水界面，以进行工程设计具有成本效益的光电催化二氧化碳还原系统。大规模利用二氧化碳和水通过太阳光驱动合成碳质燃料的最大障碍是缺乏同时高效、廉价和环境友好的催化剂。这种催化剂的发展受到了对质子耦合多重电子转移机制理解的初级阶段的阻碍，该机制涉及除CO和甲酸盐之外的CO2还原。拟议的跨学科研究将通过首次系统地研究铜和铁硫化物矿物作为新颖且廉价的光催化材料来弥补这一知识差距。建议采用一种新颖的分子共催化方法来克服二氧化碳还原成能量密集型燃料的热力学和动力学限制。目的是确定界面和本体电解质中分子助催化剂的反应机制，最终目标是开发更可持续和更高效的光合作用系统。为了实现这一雄心勃勃的目标，哥伦比亚大学的一个团队将首次研究多尺度物理和化学，利用先进的操作 FTIR 和拉曼光谱电化学、（光）电化学和理论，驱动铁和铜硫化物对碳质燃料进行人工光合作用。 （例如，密度函数理论）方法。研究期间开发的基于铜和铁硫化物的新型更高效光合作用系统将是扩大可再生能源规模的实际一步。它将为金属硫化物与水界面的合理设计带来新颖的可扩展策略。除了人工光合作用之外，这一成果还可以应用于环境修复中固定放射性核素、硫化物矿物的选矿（选择性分离）以及绿色化学品的设计。此外，这些知识将拓宽我们对生物地球化学过程的理解，包括酸性矿山排水过程、深海中铁和铜的循环，以及最终的生命起源。研究的总体结果和新方法将包含在 PI 的本科/研究生课程中。