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

项目负责人：Somasundaran， ponisseril提案编号：1336845机构：哥伦比亚大学标题：SusChEM：用于CO2光催化转化为燃料的地球丰富和无毒过渡金属硫化物的水界面的合理设计本项目重点了解地球丰富和无毒过渡金属硫化物的水界面，以设计具有成本效益的光电催化CO2还原系统。利用太阳能从二氧化碳和水合成含碳燃料的最大障碍是缺乏一种同时高效、廉价和环保的催化剂。这种催化剂的发展受到对质子耦合多电子转移参与CO和甲酸以外的CO2还原的机制理解的初级阶段的阻碍。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型廉价光催化材料来弥合这一知识差距。提出了一种新的分子共催化方法，以克服二氧化碳还原成能量密集燃料的热力学和动力学限制。目的是确定反应对界面和散装电解质中分子助催化剂的依赖机制，最终目标是开发更可持续和高效的光合系统。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使用先进的operando FTIR和拉曼光谱电化学、（照片）电化学和理论（例如密度函数理论）方法，研究驱动铁和铜硫化物对含碳燃料进行人工光合作用的多尺度物理和化学。在研究期间开发的基于铜和铁硫化物的新的更有效的光合系统将是扩大可再生能源的实际步骤。这将为合理设计金属硫化物与水的界面提供新的可扩展策略。除了人工光合作用外，这一成果还可以应用于环境修复中的放射性核素固定化，以及硫化矿物的矿物加工（选择性分离），以及更环保化学品的设计。此外，这些知识将拓宽我们对生物地球化学过程的理解，包括酸矿排水过程、深海铁和铜的循环过程，以及最终的生命起源。研究的总体结果和新方法将包括在PI的本科/研究生课程中。

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.