CAREER:Tailoring the nature of the active site of Ni electrocatalysts for electrochemical co-reduction of CO2 and H2O

职业：用于将CO2和H2O转化为合成气的稳健多相电催化剂的设计化石燃料的大量使用和由此产生的高水平CO2排放是当代的主要挑战。这些挑战的解决方案将需要开发激活反向化学途径的方法，其中CO2被转化回高能分子（即，CO和碳氢化合物燃料），使用可再生能源，如太阳能和/或风能。这些可再生能源最方便地用作电力。许多提议的处理来自化学过程的CO2的策略试图将CO2转化回碳氢化合物。将CO2和H2O转化为合成气（CO+H2）是目前不存在有效方法的一种这样的方法。合成气是制造化学品和燃料的方便原料。 韦恩州立大学的首席研究员Eranda Nikolla建议利用实验和理论技术的组合来设计稳健的电催化剂，用于使用固体氧化物电化学系统（SOEC）将CO2与H2O共还原为合成气。SOEC是电化学系统，由于在其高操作温度下有利的反应动力学，其可以促进CO2与H2O以非常高的速率同时共还原为合成气。拟议的研究将通过提供一种新的基本方法来设计强大的电催化剂，以有效地从CO2和H2O中产生合成气，从而解决能源和气候变化方面的国家重要问题，从而对推进该领域产生广泛的影响。此外，它将成为一种工具，用于（i）教育来自代表性不足群体的本科WSU工程学生，（ii）通过与当地高中，密歇根科学中心和NSF赞助的GoGirls计划的活动，促进K-12学生的STEM职业兴趣，以及（iii）通过研究和课程开发培训工程研究生。虽然使用SOEC的CO2和H2O的电化学共还原提供了很大的希望，但该领域还相当未开发。该方法的主要挑战之一是需要在高总电势下操作，这是由于与常规阴极电催化剂上的CO2和H2O的电化学还原相关的活化过电势损失（活化电化学过程所需的电势与可逆电势之间的差）。为了应对这一挑战，PI建议将联合收割机量子化学密度泛函理论（DFT）计算与实验电动力学研究相结合，以确定控制与传统电催化表面上CO2和H2O共还原相关的过电位损失的电化学步骤。目的是利用这些知识来设计改进的电催化剂，其将使共还原过程中的控制步骤的过电位损失最小化，从而提高转化过程的能量效率。拟议的工作将提供一种变革性的新方法，用于发现将CO2和H2O转化为合成气的强大而有效的电催化剂。此外，它将为PI的长期发展目标奠定基础（i）一个多功能的研究计划，广泛旨在发现有关固态电化学系统中电化学转化的机械见解，并将这些知识转化为提高性能的方法，以及（ii）旨在推进教学的跨学科教育和推广计划。关于能源和环境的培训和公众认识。

CAREER: Design of Robust Heterogeneous Electrocatalysts for Conversion of CO2 and H2O to SyngasExtensive use of fossil fuels and consequential high levels of CO2 emissions are major contemporary challenges. Solutions to these challenges will require the development of ways to activate reverse chemical pathways in which CO2 is converted back into high energy molecules (i.e., CO and hydrocarbon fuels) using renewable energy sources, such as solar and/or wind energy. These renewable energy sources are most conveniently used as electricity. Many proposed strategies for dealing with CO2 from chemical processes attempt the conversion of CO2 back to hydrocarbons. The conversion of CO2 and H2O to syngas (CO+H2) is one such process for which no efficient approach currently exists. Syngas is a convenient feedstock for making chemicals and fuels. The Principal Investigator Eranda Nikolla at Wayne State University proposes to utilize a combination of experimental and theoretical techniques to design robust electrocatalysts for the co-reduction of CO2 with H2O to syngas using solid oxide electrochemical systems (SOECs). SOECs are electrochemical systems that can facilitate the simultaneous co-reduction of CO2 with H2O to syngas with very high rates, due to the favorable reaction kinetics at their high operating temperatures. The proposed research will have a broad impact in advancing the field by providing a new fundamental methodology for designing robust electrocatalysts for efficient generation of syngas from CO2 and H2O, thereby addressing nationally important issues in energy and climate change. In addition, it will become a tool for (i) educating undergraduate WSU engineering students from underrepresented groups, (ii) promoting STEM career interest in K-12 students, through activities with local high schools, the Michigan Science Center and the NSF-sponsored GoGirls program, and (iii) training of graduate engineering students though research and course development. While electrochemical co-reduction of CO2 and H2O using SOECs offers a great deal of promise, the field is fairly unexplored. One of the main challenges with this process is the need to operate at high overall potential, due to activation overpotential losses (the difference between the potential required to activate an electrochemical process and the reversible potential) associated with the electrochemical reduction of CO2 and H2O on conventional cathode electrocatalysts. In order to address this challenge, the PI proposes to combine quantum chemical density functional theory (DFT) calculations with experimental electro-kinetic studies to identify the electrochemical steps that govern the overpotential losses associated with co-reduction of CO2 and H2O on conventional electrocatalytic surfaces. The objective is to utilize this knowledge to design improved electrocatalysts that will minimize the overpotential losses of controlling steps in the co-reduction process, thereby increasing the energy efficiency of the conversion process. The proposed work will provide a transformative new methodology for the discovery of robust and efficient electrocatalysts for conversion of CO2 and H2O to syngas. Furthermore, it will build the foundation for the PIs long-term goals of developing (i) a versatile research program, broadly aimed at discovering mechanistic insights about electrochemical transformation in solid-state electrochemical systems and translating this knowledge to ways to improve their performance, and (ii) interdisciplinary educational and outreach programs with the aim of advancing teaching, training and public awareness regarding energy and environment.