CAS: Collaborative Research: Solar CO2 Reduction by Atomically Dispersed Metal Sites on Few-Layer Carbon Nitride

CAS：合作研究：通过少层氮化碳上的原子分散金属位点减少太阳能二氧化碳

• 批准号: 2102655
• 负责人: Gonghu Li
• 金额: $ 24.37万
• 依托单位: University of New Hampshire
• 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: 2021-08-01 至 2025-01-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102655&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; Solar; CO2

With the support of the Chemical Catalysis program in the Division of Chemistry, Gonghu Li of the University of New Hampshire, N. Aaron Deskins of Worcester Polytechnic Institute and Anatoly Frenkel of Stony Brook University will study new catalysts based on earth-abundant elements to recycle carbon dioxide to produce energy-rich fuels. The catalysts will be prepared by placing isolated metal ions on a polymeric material that can absorb sunlight and stabilize the metal ions. The catalyst structure will be investigated using advanced techniques at the Brookhaven National Laboratory aided by computational modeling. This project will employ carbon dioxide as a renewable C1 feedstock and utilize light as the only energy input for this chemical transformation. Through this process, it is expected that solar energy will be converted into chemical energy and stored in the form of chemical bonds. This project focuses on fundamental research in catalysis and provides a versatile platform for training students in STEM (science, technology, engineering and mathematics) fields. The project will also provide excellent opportunities for full participation of women and underrepresented minorities in clean energy, catalysis and nanoscience.With the support of the Chemical Catalysis program in the Division of Chemistry, Drs. Gonghu Li of the University of New Hampshire, N. Aaron Deskins of Worcester Polytechnic Institute and Anatoly Frenkel of Stony Brook University will study heterogeneous photocatalysts containing molecularly defined active sites with the goal of building a system for efficient solar fuel generation. Innovative photocatalysts will be prepared by coordinating atomically dispersed cobalt sites on few-layer graphitic carbon nitride, which is to serve not only as a visible-light absorber but also a “ligand” to coordinate with and activate the cobalt centers for catalysis. The synthesized photocatalysts will be investigated using X-ray absorption fine structure (XAFS) spectroscopy and computational modeling, and evaluated in their ability to catalyze the reduction of carbon dioxide to useful chemicals and fuels. The collaborative team will focus on constructing highly active Co-N4 moieties on carbon nitride to elucidate structure-function relationships of such cobalt sites. Through the proposed studies, the research team seeks to answer fundamental questions regarding the desired structure of atomically dispersed cobalt sites on few-layer carbon nitride, the effect of carbon-doping on photocatalytic properties, and the mechanism of carbon dioxide reduction at such cobalt sites. The combined experimental and theoretical approach holds promise to improve general understanding of the structures of such catalysts and how these structures correlate with activity at the molecular level. This project has the potential to develop active catalysts for small molecule activation and solar energy conversion.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.

在化学系化学催化项目的支持下，新罕布什尔大学的Gonghu Li、伍斯特理工学院的N. Aaron Deskins和石溪大学的Anatoly Frenkel将研究基于地球丰富的元素进行回收的新型催化剂该催化剂将通过将分离的金属离子放置在可以吸收阳光并稳定金属离子的聚合物材料上来制备。将使用先进技术研究催化剂结构。在布鲁克海文国家实验室的计算模型的帮助下，该项目将采用二氧化碳作为可再生的 C1 原料，并利用光作为化学转化的唯一能源输入，预计太阳能将转化为化学能。该项目专注于催化方面的基础研究，为STEM（科学、技术、工程和数学）领域的学生提供了一个多功能的平台，也将为女性的全面参与提供绝佳的机会。以及清洁能源领域代表性不足的少数群体，在化学系化学催化项目的支持下，新罕布什尔大学的Gonghu Li博士、伍斯特理工学院的N. Aaron Deskins和石溪大学的Anatoly Frenkel将研究含有分子的异质光催化剂。确定的活性位点旨在通过协调原子分散的钴位点来制备创新的光催化剂，其目标是构建高效的太阳能燃料生成系统。在少层石墨氮化碳上，它不仅可以作为可见光吸收剂，而且可以作为与钴中心配合并激活催化作用的“配体”，将利用X射线吸收精细结构来研究合成的光催化剂。 （XAFS）光谱学和计算模型，并评估其催化二氧化碳还原为有用化学品和燃料的能力，合作团队将专注于在碳上构建高活性的 Co-N4 部分。通过拟议的研究，研究小组试图回答一些基本问题：少层碳氮化物上原子分散的钴位点的所需结构、碳掺杂对光催化性能的影响。以及此类钴位点的二氧化碳还原机制有望提高对此类催化剂结构以及这些结构与分子水平活性的关系的总体理解。开发用于小分子活化和太阳能转换的活性催化剂的潜力。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，被认为值得支持。

项目成果

X-ray Absorption Spectroscopy Studies of a Molecular CO 2 -Reduction Catalyst Deposited on Graphitic Carbon Nitride

石墨碳氮化物上沉积的分子CO 2 还原催化剂的X射线吸收光谱研究

• DOI: 10.1021/acs.jpcc.2c08587
• 发表时间: 2023-02
• 期刊: The Journal of Physical Chemistry C
• 作者: Li, Junying;Huang, Peipei;Guo, Facheng;Huang, Jiahao;Xiang, Shuting;Yang, Ke;Deskins, N. Aaron;Batista, Victor S.;Li, Gonghu;Frenkel, Anatoly I.
• 通讯作者: Frenkel, Anatoly I.

Probing active sites for carbon oxides hydrogenation on Cu/TiO2 using infrared spectroscopy

使用红外光谱探测 Cu/TiO2 上碳氧化物加氢的活性位点

• DOI: 10.1038/s42004-022-00650-2
• 发表时间: 2022-03-14
• 期刊: Communications Chemistry
• 影响因子: 5.9
• 作者: Shaaban, Ehab;Li, Gonghu
• 通讯作者: Li, Gonghu

Well-defined surface catalytic sites for solar CO 2 reduction: heterogenized molecular catalysts and single atom catalysts

用于太阳能CO 2 还原的明确表面催化位点：多相分子催化剂和单原子催化剂

• DOI: 10.1039/d3cc01821k
• 发表时间: 2023-07
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Huang, Peipei;Shaaban, Ehab;Ahmad, Esraa;St. John, Allison;Jin, Tianqi;Li, Gonghu
• 通讯作者: Li, Gonghu

Revealing the Structure of Single Cobalt Sites in Carbon Nitride for Photocatalytic CO 2 Reduction

揭示氮化碳中用于光催化 CO 2 还原的单钴位点结构

• DOI: 10.1021/acs.jpcc.2c01216
• 发表时间: 2022-05
• 期刊: The Journal of Physical Chemistry C
• 作者: Huang, Peipei;Huang, Jiahao;Li, Junying;Pham, Thang Duc;Zhang, Lei;He, Jie;Brudvig, Gary W.;Deskins, N. Aaron;Frenkel, Anatoly I.;Li, Gonghu
• 通讯作者: Li, Gonghu

Solving the structure of “single-atom” catalysts using machine learning – assisted XANES analysis

使用机器学习辅助 XANES 分析解析“单原子”催化剂的结构

• DOI: 10.1039/d1cp05513e
• 发表时间: 2022-02
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Xiang, Shuting;Huang, Peipei;Li, Junying;Liu, Yang;Marcella, Nicholas;Routh, Prahlad K.;Li, Gonghu;Frenkel, Anatoly I.
• 通讯作者: Frenkel, Anatoly I.