CAREER: Tailoring the Selectivity of Electrocatalytic Reactions in Seawater and Brine

职业：定制海水和盐水中电催化反应的选择性

• 批准号: 2344820
• 负责人: Kelsey Stoerzinger
• 金额: $ 54.97万
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-15 至 2025-12-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2344820&HistoricalAwards=false
• 关键词: CAREER; Tailoring; Selectivity; Electrocatalytic; Reactions

Renewable electricity from energy sources such as wind, solar, wave, and tidal can be used to drive chemical reactions, including the generation of hydrogen from water. The hydrogen can be further reacted with other molecules to produce chemical fuels that are more easily stored and transported compared to electrical energy. Seawater is an abundant water resource, but electrochemical hydrogen generation from seawater can generate harmful byproducts from seawater salts that pose environmental and safety concerns. The project will design and test materials and electrochemical reaction conditions that selectively promote hydrogen generation while avoiding the production of undesirable chloride-containing byproducts. The scientific outcomes will aid the development of improved energy storage and chemical manufacturing strategies that reduce our nation’s reliance on non-renewable resources. Furthermore, the research will be integrated with educational and outreach initiatives emphasizing participation by underrepresented groups.The project focuses on selective electrocatalytic water oxidation in systems containing chlorine salts. By manipulating the electronic structure of an oxide catalyst, the active sites for water and chlorine-oxidation processes will be decoupled when the pH-dependent activation of oxygen redox is triggered in highly covalent materials. This sidesteps the coupling between binding strengths of chlorine- and oxygen-containing intermediates at transition metal sites, hindering independent optimization of the reaction pathways. In situ and operando spectroscopic approaches (X-ray, vibrational) will identify adsorbed species, their dependence on applied potential and electrolyte composition, and their interaction with co-adsorbates. Comparison of adsorbate affinity with theoretical calculations will establish a tradeoff in desired reaction pathway as a function of surface energetics. Furthermore, the study will generate mechanistic understanding of the role a secondary manganese-oxide based coating atop an electrocatalyst can play in limiting the transport of chloride ions and manipulating adsorbate binding at the buried interface. Design parameters will be developed for the coatings that enable selective oxidation in brines with minimal cost to catalytic activity. The findings of the proposed work will be incorporated into undergraduate reaction engineering courses and K-12 STEM outreach programs designed to teach students about electrochemical systems. Peer teaching will be employed to solidify understanding and increase confidence in science and engineering skillsets, particularly in groups typically underrepresented in STEM.The project is supported jointly by the Catalysis program in the Division of Chemical, Bioengineering, Environmental and Transport Systems, and the Solid State and Materials Chemistry program in the Division of Materials Research.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

来自风能、太阳能、波浪能和潮汐能等能源的可再生电力可用于驱动化学反应，包括从水中产生氢气。 氢气可以进一步与其他分子反应，产生比电能更容易储存和运输的化学燃料。 海水是一种丰富的水资源，但海水电化学制氢会产生有害的海水盐副产品，造成环境和安全问题。 该项目将设计和测试材料和电化学反应条件，以选择性地促进氢气生成，同时避免产生不希望的含氯化物的副产品。科学成果将有助于改进能源储存和化学制造战略的发展，减少我们国家对不可再生资源的依赖。此外，这项研究将与教育和推广活动结合起来，强调代表性不足的群体的参与，该项目的重点是含氯盐系统中的选择性电催化水氧化。通过操纵氧化物催化剂的电子结构，当在高度共价材料中触发氧氧化还原的pH依赖性活化时，水和氯氧化过程的活性位点将被解耦。这回避了过渡金属位点处含氯和含氧中间体的结合强度之间的耦合，阻碍了反应途径的独立优化。在原位和operando光谱方法（X射线，振动）将确定吸附的物种，其依赖于所施加的电位和电解质组合物，以及它们与共吸附物的相互作用。吸附物亲和力与理论计算的比较将建立所需的反应途径作为表面能的函数的权衡。此外，该研究将产生的作用的机械理解的二次锰氧化物为基础的涂层顶部的电催化剂可以发挥限制氯离子的运输和操纵吸附结合在埋界面。将开发涂层的设计参数，使选择性氧化在盐水中的催化活性的成本最小。拟议工作的结果将被纳入本科反应工程课程和K-12 STEM推广计划，旨在向学生传授电化学系统。将采用同伴教学来巩固理解和增加对科学和工程技能的信心，特别是在通常在STEM中代表性不足的群体中。该项目由化学，生物工程，环境和运输系统部门的催化计划联合支持，以及材料研究部的固态和材料化学计划。该奖项反映了NSF的法定使命，并已被视为通过使用基金会的知识价值和更广泛的影响审查标准进行评估，

项目成果

Breaking OER and CER scaling relations via strain and its relaxation in RuO2 (101)

通过 RuO2 (101) 中的应变及其弛豫打破 OER 和 CER 标度关系

• DOI: 10.1016/j.mtener.2022.101087
• 发表时间: 2022
• 期刊: Materials Today Energy
• 影响因子: 9.3
• 作者: Adiga, Prajwal;Nunn, William;Wong, Cindy;Manjeshwar, Anusha K.;Nair, Sreejith;Jalan, Bharat;Stoerzinger, Kelsey A.
• 通讯作者: Stoerzinger, Kelsey A.