Collaborative Research: Visible-Light-Augmented Reverse Water Gas Shift Reaction on Hybrid Plasmonic Photocatalysts

合作研究：混合等离子体光催化剂上的可见光增强反向水煤气变换反应

• 批准号: 2102239
• 负责人: Alan Bristow
• 金额: $ 23.69万
• 依托单位: West Virginia University Research Corporation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102239&HistoricalAwards=false
• 关键词: Collaborative; Research; Visible; Light; Augmented

Photocatalysis is an attractive technology for the sustainable, solar-driven chemical conversion of greenhouse gases, such as carbon dioxide, to value-added fuels and chemicals. To this end, the project explores the selective photocatalytic reduction of carbon dioxide by hydrogen into carbon monoxide and water. This reaction is also known as the reverse water-gas shift reaction (RWGS). The carbon monoxide product can be further transformed into a range of high-value chemicals and fuels. Among the earth-abundant metal and metal oxide materials that can serve as a catalyst for this reaction, copper-based nanocatalysts have emerged as one of the best candidates for the RWGS reaction. However, under conventional thermal energy-driven catalytic conditions, the copper nanocatalysts require relatively high operating reaction temperatures and suffer from less than desirable product selectivity. This research project aims to develop a novel photocatalytic approach to achieving superior catalytic activity and desired-product selectivity for the RWGS reaction. The project also demonstrates sustainable energy concepts to local elementary and high school students through various outreach activities, including Chemkidz events at schools across Oklahoma, Summer Science Camp in Appalachia (West Virginia), and National Lab Day events at the Oklahoma State University and West Virginia University campuses.In conventional catalytic processes, the dissipation of thermal energy drives the transformation of reactants on the surface of catalysts toward a variety of products. Challenges remain, however, for designing catalysts that can drive the breakage and formation of specific chemical bonds toward desirable products with the utmost selectivity. This research project develops a hybrid plasmonic photocatalytic approach for this purpose. Hybrid plasmonic photocatalysts consist of light-absorbing plasmonic metals surrounded by catalytic metals or metal oxides. The hybrid plasmonic photocatalytic approach offers a unique opportunity to control catalytic activity and selectivity using photon stimuli as an additional degree of freedom. In hybrid plasmonic photocatalysts, such as Cu core/Cu2O shell, the electron transfer from the Cu core to the Cu2O shell can occur by Landau damping-mediated hot-electron-transfer pathway or by chemical interface damping (CID). Although a fundamental understanding of the Landau damping-mediated hot-electron-transfer pathway is well established, design rules for the chemical interface damping pathway remain unknown. This collaborative project will develop design rules for chemical interface damping-induced electron-driven photochemistry. These rules will then be applied to the design of core/shell, Cu/Cu2O and Ag/Cu2O photocatalysts for the RWGS reaction. This research project also aims to distinguish the role of chemical interface damping- and Landau damping-mediated electron-transfer pathways in hybrid plasmonic photocatalysts using photocatalytic rate and quantum efficiency measurements and in-situ femtosecond transient-absorption spectroscopy. It is hypothesized that the chemical interface damping pathway will exhibit higher quantum efficiency and minimal local heating effects compared to the Landau damping pathway. Also, beyond the focus on Cu/Cu2O and Ag/Cu2O core/shell photocatalysts for the RWGS reaction, the design rules developed in this project can be applied to a wide range of other hybrid plasmonic nanostructures for photocatalytic and photovoltaic applications.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.

光催化是一种有吸引力的技术，可用于将二氧化碳等温室气体可持续地、由太阳能驱动的化学转化为增值燃料和化学品。为此，该项目探索了氢气选择性光催化还原二氧化碳为一氧化碳和水。该反应也称为逆水煤气变换反应(RWGS)。一氧化碳产品可以进一步转化为一系列高价值的化学品和燃料。在地球上丰富的金属和金属氧化物材料中，铜基纳米催化剂已经成为RWGS反应的最佳候选者之一。然而，在传统的热能驱动的催化条件下，铜纳米催化剂需要较高的操作反应温度，并且产品选择性较差。本研究项目旨在开发一种新的光催化方法，以实现RWGS反应的优异催化活性和期望的产物选择性。该项目还通过各种外展活动向当地中小学生展示可持续能源的概念，包括俄克拉荷马州各学校的Chemystz活动，阿巴拉契亚(西弗吉尼亚州)的夏季科学夏令营，以及俄克拉荷马州立大学和西弗吉尼亚大学校园的国家实验室日活动。在传统的催化过程中，热能的耗散驱动催化剂表面的反应物转化为各种产品。然而，在设计催化剂方面仍然存在挑战，这些催化剂能够以最大的选择性推动特定化学键的断裂和形成，以获得理想的产品。本研究项目为此目的开发了一种混合等离子体光催化方法。复合等离子体光催化剂是由吸收光的等离子体金属与催化金属或金属氧化物复合而成。混合等离子体光催化方法提供了一个独特的机会，利用光子刺激作为额外的自由度来控制催化活性和选择性。在杂化等离子体光催化剂中，如铜核/Cu2O壳层，电子从铜核到Cu2O壳层的转移可以通过朗道阻尼法或化学界面阻尼法进行。尽管对朗道阻尼介导的热电子转移途径已有了基本的了解，但化学界面阻尼途径的设计规则仍然未知。这个合作项目将开发化学界面阻尼诱导的电子驱动光化学的设计规则。这些规则将应用于RWGS反应的核/壳、铜/Cu2O和Ag/Cu2O光催化剂的设计。本研究项目还旨在通过光催化速率和量子效率的测量以及原位飞秒瞬时吸收光谱来区分化学界面阻尼型和朗道阻尼型电子转移通路在杂化等离子体光催化剂中的作用。假设与朗道阻尼器相比，化学界面阻尼器具有更高的量子效率和最小的局部加热效应。此外，除了关注用于RWGS反应的铜/Cu2O和Ag/Cu2O核/壳光催化剂外，该项目中开发的设计规则还可以应用于广泛的其他用于光催化和光伏应用的混合等离子体纳米结构。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。