Collaborative Research: Solar-Driven Hydrogenation of CO2 using Hierarchically Porous TiO2 with Spatially Isolated Au and Pt Nanoparticles

合作研究：利用分级多孔 TiO2 与空间隔离的 Au 和 Pt 纳米粒子进行太阳能驱动的 CO2 氢化

• 批准号: 1705566
• 负责人: Jie He
• 金额: $ 23.01万
• 依托单位: University of Connecticut
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-15 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1705566&HistoricalAwards=false
• 关键词: Collaborative; Research; Solar; Driven; Hydrogenation

Solar-powered production of fuels such as methanol from carbon dioxide (CO2) offers the potential to enable solar power, which is available on a transient basis, to be stored in the form of a chemical fuel for transport and other applications. Efficient and cost-effective production of solar fuels remains a scientific and technological challenge with issues of efficiency, cost, and materials durability. This collaborative project aims to design innovative materials that are capable of converting carbon dioxide and hydrogen to methanol using natural sunlight as the only energy input. This class of materials will consist of multiple components, including two types of metal nanoparticle catalysts that are separately placed within porous nanostructures of the catalyst system. By harvesting light, one of the metal nanoparticle catalyst will produce both heat and hot electrons to activate the carbon dioxide molecules. The other metal catalyst will split hydrogen molecules into hydrogen atoms, which are also needed for converting carbon dioxide to methanol. Results obtained through this project will offer fundamental insights and practical guidelines to achieving low-temperature conversion of carbon dioxide to liquid fuels using solar energy. The research will be incorporated into outreach activities for high school teachers and students as well as summer research activities for undergraduate students. Workshops on nanoscience and clean energy will be designed and offered to local high school students and K-12 science teachers in the New England area. Among the methods for carbon dioxide utilization, hydrogenation which employs dihydrogen as an electron donor and proton source to reduce carbon dioxide to high-value fuels is of particular interest, due to its sustainability and low environmental impact. Hydrogenation of carbon dioxide, however, often requires operation at high temperature because a large energy input is needed to activate carbon dioxide, even in the presence of catalysts. The focus of this collaborative effort is to design a new class of hierarchical hybrid photocatalysts that can harness visible light to mediate hydrogenation of carbon dioxide at room temperature. The first objective of this project is to synthesize hybrid photocatalysts consisting of porous titanium dioxides and spatially isolated nanoparticles of Au and Pt. The plasmonic Au nanoparticles will harvest visible light and subsequently convert photons to thermal energy and generate hot electrons for carbon dioxide activation. The Pt nanoparticles will facilitate hydrogen adsorption and dissociation. The second objective of this project is to investigate the hybrid photocatalysts in cooperatively catalyzing carbon dioxide activation and hydrogen spillover to achieve solar hydrogenation of carbon dioxide. Mechanistic studies using in situ infrared spectroscopic studies will be conducted to establish correlations between nanostructures of the hybrid materials and their catalytic performance. The outcome of solar-driven hydrogenation using these hybrid photocatalysts will illustrate a new pathway to convert carbon dioxide to liquid fuels by utilizing renewable energy sources.

利用太阳能生产二氧化碳 (CO2) 等甲醇等燃料，有可能使太阳能（短暂可用）以化学燃料的形式储存起来，用于运输和其他应用。太阳能燃料的高效且具有成本效益的生产仍然是一项科学和技术挑战，涉及效率、成本和材料耐久性问题。该合作项目旨在设计能够利用自然阳光作为唯一能量输入将二氧化碳和氢气转化为甲醇的创新材料。此类材料将由多种成分组成，包括两种类型的金属纳米粒子催化剂，它们分别放置在催化剂系统的多孔纳米结构内。通过收集光，其中一种金属纳米粒子催化剂将产生热量和热电子来激活二氧化碳分子。另一种金属催化剂会将氢分子分解成氢原子，这也是将二氧化碳转化为甲醇所必需的。通过该项目获得的结果将为利用太阳能实现二氧化碳低温转化为液体燃料提供基本见解和实用指南。该研究将纳入高中师生的外展活动以及本科生的暑期研究活动。将为新英格兰地区的当地高中生和 K-12 科学教师设计并提供有关纳米科学和清洁能源的研讨会。 在二氧化碳利用方法中，利用氢气作为电子供体和质子源将二氧化碳还原为高价值燃料的加氢因其可持续性和低环境影响而受到特别关注。然而，二氧化碳的氢化通常需要在高温下操作，因为即使在催化剂存在下也需要大量的能量输入来活化二氧化碳。这项合作的重点是设计一种新型的分层混合光催化剂，它可以利用可见光在室温下介导二氧化碳的氢化。该项目的第一个目标是合成由多孔二氧化钛和空间隔离的金和铂纳米颗粒组成的混合光催化剂。等离激元金纳米颗粒将收集可见光，随后将光子转化为热能，并产生用于活化二氧化碳的热电子。 Pt 纳米粒子将促进氢的吸附和解离。该项目的第二个目标是研究混合光催化剂协同催化二氧化碳活化和氢气溢出以实现二氧化碳的太阳能加氢。将使用原位红外光谱研究进行机理研究，以确定杂化材料的纳米结构与其催化性能之间的相关性。使用这些混合光催化剂的太阳能驱动氢化的结果将说明利用可再生能源将二氧化碳转化为液体燃料的新途径。

项目成果

N-Heterocyclic carbene-ended polymers as surface ligands of plasmonic metal nanoparticles

N-杂环卡宾末端聚合物作为等离子体金属纳米粒子的表面配体

• DOI: 10.1039/c9tc04776j
• 发表时间: 2020-02-20
• 期刊: Journal of Materials Chemistry C
• 影响因子: 6.4
• 作者: Srinivas Thanneeru;Kaitlynn M. Ayers;Murali Anuganti;Lei Zhang;C. Kumar;G. Ung;Jie He
• 通讯作者: Jie He

Self-limiting growth of ligand-free ultrasmall bimetallic nanoparticles on carbon through under temperature reduction for highly efficient methanol electrooxidation and selective hydrogenation

通过低温还原实现碳上无配体超小双金属纳米粒子的自限性生长，用于高效甲醇电氧化和选择性加氢

• DOI: 10.1016/j.apcatb.2019.118553
• 发表时间: 2020-05-05
• 期刊: Applied Catalysis B-environmental
• 影响因子: 22.1
• 作者: Mingzhen Hu;Lei Jin;Yuanyuan Zhu;Lei Zhang;Xingxu Lu;Peter Kerns;Xingsong Su;Sen Cao;P. Gao
• 通讯作者: P. Gao

Symmetry-Broken Patches on Gold Nanoparticles through Deficient Ligand Exchange

通过缺陷配体交换导致金纳米颗粒上对称性破坏的斑块

• DOI: 10.1021/acsmacrolett.1c00252
• 发表时间: 2021-07
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Duan, Hanyi;Luo, Qiang;Wei, Zichao;Lin, Yao;He, Jie
• 通讯作者: He, Jie

Direct growth of ultrasmall bimetallic AuPd nanoparticles supported on nitrided carbon towards ethanol electrooxidation

氮化碳负载超小型双金属 AuPd 纳米颗粒直接生长用于乙醇电氧化

• DOI: 10.1016/j.electacta.2018.03.017
• 发表时间: 2018-04-10
• 期刊: Electrochimica Acta
• 影响因子: 6.6
• 作者: Yue Yang;Lei Jin;Ben Liu;Peter Kerns;Jie He
• 通讯作者: Jie He

Oxidative nucleation and growth of Janus-type MnOx-Ag and MnOx-AgI nanoparticles

Janus 型 MnOx-Ag 和 MnOx-AgI 纳米颗粒的氧化成核和生长

• DOI: 10.1039/c9nr03787j
• 发表时间: 2019-01
• 期刊: Nanoscale
• 影响因子: 6.7
• 作者: Zhang, Lei;Jin, Lei;Yang, Yue;Kerns, Peter;Su, Xingsong;Meng, Michael;Liu, Ben;He, Jie
• 通讯作者: He, Jie