UNS:Collaborative Research: Investigating Interfacial Sites in Metal/TiO2 Photocatalysts with in situ Spectroscopy and Computational Modeling

1510810(Li)和Amp；1511672(Deskins)这项合作研究专注于基于金属/二氧化钛纳米复合材料的光催化剂的基础研究。二氧化钛光催化剂在水/空气净化和太阳能发电中得到了广泛的研究。在二氧化钛表面沉积金属纳米颗粒可以极大地提高光子能量的利用率，从而实现靶向表面反应。然而，关于金属和二氧化钛之间界面区域中催化中心的确切结构和功能，人们知之甚少。这项研究可能会导致更好地设计基于富含地球的元素的创新半导体光催化剂，以实现高效的太阳能转换。该项目还将支持向公众广泛和有效地传播可持续发展概念的教育活动，并为妇女和代表性不足的少数群体充分参与STEM领域提供机会。本项目的具体目的是研究界面低配位金属中心如何改变(I)铜/二氧化钛的产物选择性和(Ii)TiN/二氧化钛纳米复合材料在光催化还原二氧化碳为燃料中的反应活性。金属/二氧化钛纳米复合材料在太阳光催化中表现出更高的反应活性。关于界面位置的知识对光催化研究很重要，但目前对它的了解有限，缺乏坚实的理论基础。在本项目中，将使用无机和有机金属前驱体合成合理设计的界面位置，并通过多种技术组合对其进行广泛表征，并对其光催化还原二氧化碳进行评估。用原位光谱技术(FTIR和EPR)和计算模拟(密度泛函理论)研究了合成界面位的结构和功能。通过拟议的研究，PI希望建立界面位置的结构-功能关系，这些关系也适用于许多其他(光)催化体系。潜在研究的技术对光催化的理解和商业化应用具有重要意义。尤其重要的是理论和实验之间的联系，这有可能推动技术进步，超越拟议工作中探讨的二氧化碳减少的具体例子。PIS建议通过本科生指导和课程开发将他们的研究与教育相结合。从事这一拟议研究项目的学生将在一个对可持续能源未来和减少温室气体排放非常重要的领域接受跨学科培训。

1510810(Li) & 1511672 (Deskins)This collaborative research is focused on fundamental studies of photocatalysts based on metal/titania nanocomposites. Titania photocatalysts have been extensively studied in water/air purification and solar fuel generation. Depositing metal nanoparticles on titania surfaces can greatly improve the utilization of photonic energy in carrying out targeted surface reactions. However, little is known about the exact structure and function of catalytic sites in the interfacial region between the metal and titania phases. This research will potentially lead to better design of innovative semiconductor photocatalysts based on earth-abundant elements for efficient solar energy conversion. The project will also support educational activities to broadly and effectively disseminate sustainability concepts to the public, and provide opportunities for full participation of women and underrepresented minorities in STEM fields. The specific aim of this project is to investigate how interfacial, low coordination metal sites alter (i) product selectivity of copper/titania and (ii) reactivity of tin/titania nanocomposites in photocatalytic reduction of carbon dioxide into fuels. Metal/titania nanocomposites containing interfaces between individual components have demonstrated enhanced reactivity in solar photocatalysis. Knowledge regarding interfacial sites is important for photocatalysis research, but understanding is currently limited and without strong theoretical basis. In this project, rationally designed interfacial sites will be synthesized using inorganic and organometallic precursors, extensively characterized with a combination of techniques, and evaluated in photocatalytic carbon dioxide reduction. The structure and function of the synthesized interfacial sites will be investigated using in situ spectroscopic techniques (FTIR and EPR) and computational modeling (density functional theory). Through the proposed research, the PIs hope to establish structure-function relationships for interfacial sites that are also applicable to many other (photo)catalytic systems. The technology investigated potentially is very important to the understanding and commercial application of photocatalysis. Especially important is the link between theory and experiment which has the potential to advance technology beyond the specific example of carbon dioxide reduction explored in the proposed work. The PIs propose to integrate their research with education via undergraduate mentoring and curriculum development. Students working on the proposed research project will receive interdisciplinary training in a field of great importance toward a sustainable energy future and reduced greenhouse gas generation.