CAREER: Rational Design of Defect-Ordered Architectures in Oxygen-Deficient Perovskites to Control the Oxygen-Evolution Activity

非技术综述：可用于能源相关工艺和设备的新材料的发现对全球能源格局、繁荣和福利的未来具有重大影响。例如，需要具有特定性质的新材料，以更好地促进将水分解为基本成分，这对从可再生资源中生产氢气和氧气非常重要。另一个同样重要的性质是某些固体材料中的电荷传导，这一现象对许多能源设备(如电池和燃料电池)来说是必不可少的。研究这些属性的基本方面是这个职业奖项的中心。该奖项由材料研究部的固体和材料化学计划、现有的激励竞争研究计划(EPSCoR)和化学部的化学催化计划共同支持。在这一奖项下，Ramezanipour教授的研究小组开发了合理设计功能材料的指导方针，其中重要的与能量相关的性质通过改变化合物中原子的排列来控制和修改。该项目促进了对功能材料的基本了解，并导致发现了有助于能源相关应用领域的科学和技术进步的新化合物。此外，作为该奖项的一部分，一项教育计划帮助学生提高他们的实验室技能，促进他们的学术成功，并为他们在需要实验室专业知识的领域的潜在职业生涯做好准备。此外，针对少数族裔学生的外展活动向这些学生介绍基础研究，提高他们的科学素养，并激发他们对化学的兴趣。这些外展活动，以及女学生参与实践研究的实习计划，扩大了该项目的影响，并有助于增加STEM领域的多样性。技术摘要：在材料研究部固体和材料化学计划、已建立的激发竞争研究计划(EPSCoR)和化学系化学催化计划的共同支持下，研究人员努力揭示允许合理设计和合成缺陷有序结构的基本参数，以及缺陷排列对功能性质的影响，特别是电荷传输和放氧活性。重点是设计和合成缺陷有序缺氧型钙钛矿，这些钙钛矿在分解水的析氧反应(OER)中表现出优异的电催化活性。到目前为止，控制其OER活动的基本结构-财产关系在很大程度上仍未得到探索。这类材料的关键特征是由于缺氧而产生的缺陷的存在。缺陷的不同排列导致了不同类型的有序结构。在这里，Ramezanipour教授和他的团队研究了如何控制缺陷的排列和有序性，并探索了缺陷排列在指导缺氧钙钛矿OER活性中的作用。此外，他们还研究了缺陷排列和电荷传输之间的关系，这是影响OER活性的另一个性质。总体而言，这种多方面和全面的方法涉及结构顺序、价态、电子结构、电荷传输的变化以及这些参数对OER性质的影响的材料设计、综合和研究。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

NON-TECHNICAL SUMMARY:Discovery of new materials that can be used in energy-related processes and devices has a major impact on the future of global energy landscape, prosperity and welfare. For example, new materials with specific properties are needed to better facilitate splitting of water into its basic components, which is important for the generation of hydrogen and oxygen from renewable sources. A similarly important property is the conduction of charges in certain solid materials, a phenomenon that is essential to many energy devices such as batteries and fuel cells. Studying fundamental aspects of these properties is at the center of this CAREER award. The award is jointly supported by the Solid State and Materials Chemistry program in the Division of Materials Research, the Established Program to Stimulate Competitive Research (EPSCoR), and the Chemical Catalysis Program in the Division of Chemistry. Under this award the research group of Prof. Ramezanipour develops guidelines for rational design of functional materials, where important energy-related properties are controlled and modified by changing the arrangements of atoms within the compounds. This project advances fundamental understanding of functional materials and results in discovery of novel compounds that contribute to the progress of science and technology in the field of energy-related applications. In addition, as part of this award an educational plan helps students to enhance their laboratory skills, facilitates their academic success, and prepares them for potential careers in areas that require expertise in a laboratory setting. Furthermore, outreach activities for underrepresented minority students introduce these students to basic research, increase the scientific literacy, and spark interest in chemistry. These outreach activities, and an internship program for female students to participate in hands-on research, broaden the impact of the project and help increase diversity in STEM fields.TECHNICAL SUMMARY:With this CAREER award, jointly supported by the Solid State and Materials Chemistry program in the Division of Materials Research, the Established Program to Stimulate Competitive Research (EPSCoR), and the Chemical Catalysis Program in the Division of Chemistry, researchers work to uncover the fundamental parameters that allow for rational design and synthesis of defect-ordered architectures and the impact of defect-arrangement on functional properties, in particular the charge-transport and oxygen-evolution activity. The specific focus is on design and synthesis of defect-ordered oxygen-deficient perovskites, which have recently shown outstanding electrocatalytic activity for oxygen-evolution reaction (OER) of water splitting. Until now the fundamental structure-property relationships that control their OER activity have remained largely unexplored. The key characteristic of this class of materials is the presence of defects, created due to oxygen-deficiency. Various arrangements of defects lead to different types of ordered structures. Here Prof. Ramezanipour and his group investigate how the arrangement and ordering of defects can be controlled and explore the role of defect-arrangement in directing the OER activity of oxygen-deficient perovskites. In addition, they investigate the relationship between defect-arrangement and charge-transport, which is another property that affects the OER activity. Overall, the multifaceted and comprehensive approach involves material design, synthesis and study of the changes in structural order, valence-state, electronic structure, charge-transport, and the impact these parameters have on OER properties.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.