EAGER: Collaborative Research: Hybrid Quantum Dot-Metal Nanocrystals for Photoreduction of CO2: Synthesis, Spectroscopy and Catalysis

EAGER：合作研究：用于二氧化碳光还原的混合量子点金属纳米晶体：合成、光谱学和催化

• 批准号: 1936228
• 负责人: Jie He
• 金额: $ 15万
• 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: 2019
• 资助国家: 美国
• 起止时间: 2019-08-15 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1936228&HistoricalAwards=false
• 关键词: EAGER; Collaborative; Research; Hybrid; Quantum

Efficient, sustainable, and cost-effective reaction of combustion-generated carbon dioxide to fuels and chemicals remains one of the leading technical challenges of our times. Among sustainable technologies, the direct conversion of solar energy to chemical energy, as accelerated by catalytic materials, is one of the most attractive options, but is limited by the efficiency of the solar-to-chemical energy conversion. The project will investigate a new combination of catalytic materials, and methods for structuring those materials, that has potential to further increase both the rate and efficiency of solar-driven carbon dioxide reactions. The study also utilizes an ultrafast spectroscopic technique that may shed new light on the energy conversion process - knowledge that can be extended to a wide range of applications beyond photocatalysis. The project will generate insight that supports technologies critical to our nation's future energy security while decreasing carbon emissions.Energy sustainability and environmental protection has created an urgent need to develop new methods that efficiently, selectively, and sustainably convert carbon dioxide (CO2) into valuable chemicals and fuels. Among existing technologies, solar-driven photoreduction and transformation of CO2 into carbon-based fuels represents an attractive method due to its sustainability and its minimal environmental impact. High-performance photocatalysts are the key to achieving effective CO2 photoreduction. The collaborative project will perform proof-of-principle studies of novel nanocatalysts for solar-driven CO2 photoreduction based on hybrids of semiconductor core@shell quantum dots (QDs, e.g., CdSe@CdS) and gold (Au) nanoparticles (NPs). CdSe@CdS core-shell QDs can efficiently capture solar energy in the entire ultraviolet and most of the visible spectral range due to their low bandgap of 1.9 eV as well as having a highly reductive conduction band. Meanwhile, Au NPs show high CO2 binding affinity and excellent reaction selectivity (e.g., CO2 to CO). Coupling CdSe@CdS semiconductor QDs with Au NPs through direct epitaxial growth has the potential to greatly improve the overall conversion efficiency of solar energy to chemical fuels. To this end, the project will explore new synthetic methods towards synthesizing QD-metal hybrid nanomaterials with precise control over size, shape, geometry, and lattice strain. The unique HNC structures make it possible to efficiently transfer multiple electrons as quantitatively detected by ultrafast transient absorption spectroscopy, thereby providing fundamental understanding of the relationships between structural parameters and charge separation/transfer processes between the QDs and Au, as well as photocatalytic performance of QD-Au. Beyond the technical aspects of the project, the investigators will collaborate in organizing annual events such as workshops and outreach days featuring nanoscience and clean energy at both universities. The outreach activities will be designed to stimulate the interests of students from high schools in pursing STEM-related higher education. In addition, scientific symposia will be organized with the goal of highlighting research opportunities related to photocatalytic CO2 reduction.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.

燃烧产生的二氧化碳与燃料和化学品的高效、可持续且经济高效的反应仍然是我们这个时代的主要技术挑战之一。 在可持续技术中，通过催化材料加速将太阳能直接转化为化学能是最有吸引力的选择之一，但受到太阳能到化学能转化效率的限制。 该项目将研究催化材料的新组合以及构建这些材料的方法，有可能进一步提高太阳能驱动的二氧化碳反应的速率和效率。 该研究还利用了超快光谱技术，该技术可能为能量转换过程提供新的线索——这些知识可以扩展到光催化以外的广泛应用。 该项目将产生见解，支持对我们国家未来能源安全至关重要的技术，同时减少碳排放。能源可持续性和环境保护迫切需要开发新方法，以有效、选择性和可持续地将二氧化碳 (CO2) 转化为有价值的化学品和燃料。 在现有技术中，太阳能驱动的光还原和将二氧化碳转化为碳基燃料由于其可持续性和对环境影响最小而成为一种有吸引力的方法。高性能光催化剂是实现有效二氧化碳光还原的关键。该合作项目将基于半导体核壳量子点（QD，例如 CdSe@CdS）和金（Au）纳米颗粒（NP）的混合体，对用于太阳能驱动的二氧化碳光还原的新型纳米催化剂进行原理验证研究。 CdSe@CdS核壳量子点由于其1.9 eV的低带隙以及高还原性导带，可以有效捕获整个紫外和大部分可见光谱范围内的太阳能。同时，Au NPs 表现出高 CO2 结合亲和力和优异的反应选择性（例如，CO2 到 CO）。 通过直接外延生长将CdSe@CdS半导体量子点与Au NPs耦合有可能大大提高太阳能到化学燃料的整体转换效率。 为此，该项目将探索新的合成方法，以精确控制尺寸、形状、几何形状和晶格应变来合成量子点-金属杂化纳米材料。 独特的HNC结构使得超快瞬态吸收光谱定量检测的多个电子的有效转移成为可能，从而提供对QD和Au之间的结构参数和电荷分离/转移过程之间的关系以及QD的光催化性能的基本了解-金。 除了该项目的技术方面之外，研究人员还将合作组织年度活动，例如在两所大学举办以纳米科学和清洁能源为主题的研讨会和外展日。外展活动旨在激发高中生追求 STEM 相关高等教育的兴趣。 此外，还将组织科学研讨会，旨在突出与光催化二氧化碳减排相关的研究机会。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，认为值得支持。

项目成果

Colloidal Assembly of Au–Quantum Dot–Au Sandwiched Nanostructures with Strong Plasmon–Exciton Coupling

具有强等离子体激子耦合的金-量子点-金夹层纳米结构的胶体组装

• DOI: 10.1021/acs.jpclett.0c00110
• 发表时间: 2020-04
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Luo, Yi;Wang, Yongchen;Liu, Muqiong;Zhu, Hua;Chen, Ou;Zou, Shengli;Zhao, Jing
• 通讯作者: Zhao, Jing

Surface Basicity of Metal@TiO 2 to Enhance Photocatalytic Efficiency for CO 2 Reduction

金属@TiO 2 的表面碱度可提高光催化CO 2 还原效率

• DOI: 10.1021/acsami.1c09119
• 发表时间: 2021-08
• 期刊: ACS Applied Materials & Interfaces
• 影响因子: 9.5
• 作者: Jin, Lei;Shaaban, Ehab;Bamonte, Scott;Cintron, Daniel;Shuster, Seth;Zhang, Lei;Li, Gonghu;He, Jie
• 通讯作者: He, Jie

Do polymer ligands block the catalysis of metal nanoparticles? Unexpected importance of binding motifs in improving catalytic activity

• DOI: 10.1039/d0ta03906c
• 发表时间: 2020-08-11
• 期刊: Journal of Materials Chemistry
• 作者: Lei Zhang;Zichao Wei;Michael Meng;G. Ung;Jie He
• 通讯作者: Jie He

Crystalline Mesoporous Complex Oxides: Porosity‐Controlled Electromagnetic Response

结晶介孔复合氧化物：孔隙率——受控的电磁响应

• DOI: 10.1002/adfm.201909491
• 发表时间: 2020-02
• 期刊: Advanced Functional Materials
• 影响因子: 19
• 作者: Jin, Lei;Su, Xingsong;Shi, Jianhang;Shih, Kuo‐Chih;Cintron, Daniel;Cai, Tong;Nieh, Mu‐Ping;Chen, Ou;Suib, Steven L.;Jain, Menka;et al
• 通讯作者: et al

Highly Crystalline Mesoporous Titania Loaded with Monodispersed Gold Nanoparticles: Controllable Metal–Support Interaction in Porous Materials

负载单分散金纳米粒子的高结晶介孔二氧化钛：可控金属——支持多孔材料中的相互作用

• DOI: 10.1021/acsami.9b20231
• 发表时间: 2020-01
• 期刊: ACS Applied Materials & Interfaces
• 影响因子: 9.5
• 作者: Jin, Lei;Liu, Ben;Louis, Michael E.;Li, Gonghu;He, Jie
• 通讯作者: He, Jie