Collaborative Research: CAS: Carbene-Containing Ligands on Cu and Cu3N Nanocubes: Access to Stable and Selective Electrolysis for CO2 Reduction

合作研究：CAS：Cu 和 Cu3N 纳米立方体上的含卡宾配体：获得稳定和选择性电解以还原 CO2

• 批准号: 2102290
• 负责人: Shouheng Sun
• 金额: $ 27万
• 依托单位: Brown University
• 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=2102290&HistoricalAwards=false
• 关键词: Collaborative; Research; CAS; Carbene; Containing

With the support of the Chemical Catalysis program in the Division of Chemistry, Professors He and Ung at the University of Connecticut and Professor Sun at Brown University are designing new hybrid materials for selective electrochemical activation of carbon dioxide (CO2). The team will utilize synthetic polymers to coat and protect copper-based catalysts, allowing the resulting hybrid materials to be more robust and efficient for CO2 electroreduction to yield value-added hydrocarbon products. The use of renewable electricity to convert CO2 to useful chemical products is likely to be an important component of sustainability. This collaborative project will involve undergraduate, graduate, and postgraduate researchers from two universities, and will utilize each groups’ expertise in polymer, nanomaterial, organometallic, surface science, and electrochemistry. The results obtained from this project will be disseminated to science and engineering students through joint meetings, courses, undergraduate research activities, and outreach activities. The PIs are collaborating with local high schools and outreach programs in the southern New England region to attract students into studies and potential career paths in STEM (science, technology, engineering and mathematics) fields.With the support of the Chemical Catalysis program in the Division of Chemistry, Professors He and Ung at the University of Connecticut and Professor Sun at Brown University are studying new Cu-based nanocubes functionalized with synthetic polymer ligands toward stable and selective electroreduction of CO2. The central hypothesis of this proposal is twofold: i) the incorporation of Cu-based nanocubes with rationally designed synthetic polymers to prevent interparticle coalescence and surface corrosion during electroreduction, and ii) hydrophobic polymer ligands to control the microenvironment of nanocubes and improve the selectivity of nanocubes. Polymer ligands terminated with N-heterocyclic carbenes (NHCs) will be anchored on Cu, copper nitride (Cu3N) and core-shell Cu/Cu3N nanocubes through stable NHC-Cu bonds. Those nanocubes have maximum (100) surface exposure to efficiently promote C-C coupling and form C2+ hydrocarbon products. Polymer NHC ligands will balance the localized proton concentration nearby the surface of nanocubes through control over polymer chain lengths and hydrophobicity to achieve maximum catalytic proton-assisted CO2 reduction to C-C coupling products and minimize proton reduction reaction. The Cu-NHC bond stability and the structural integrity of polymer-grafted Cu and Cu3N nanocubes will be probed using in situ spectroscopies and microscopies. The polymer chain length dependent diffusion properties will be quantitatively measured and correlated to the catalytic performance of Cu and Cu3N nanocubes. The successful demonstration of the active and efficient polymer NHC-Cu nanocubes for CO2 electroreduction also allows tackling more broadly the long-term stability issues of all other cathodic nanocatalysts to improve the sustainability of electroreduction.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，康涅狄格大学的 He 教授和 Ung 教授以及布朗大学的 Sun 教授正在设计用于选择性电化学活化二氧化碳（CO2）的新型混合材料，该团队将利用合成材料。聚合物来涂覆和保护铜基催化剂，使所得的混合材料能够更加坚固和有效地进行二氧化碳电还原，从而产生增值的碳氢化合物产品，使用可再生电力将二氧化碳转化为有用的化学产品可能是一个重要的技术。成分该合作项目将涉及两所大学的本科生、研究生和研究生研究人员，并将利用每个小组在聚合物、纳米材料、有机金属、表面科学和电化学方面的专业知识，该项目获得的成果将被传播到科学领域。 PI 正在与新英格兰南部地区的当地高中和外展项目合作，吸引学生进入 STEM（科学、技术、工程和在化学系化学催化项目的支持下，康涅狄格大学的 He 和 Ung 教授以及布朗大学的 Sun 教授正在研究用合成聚合物配体功能化的新型铜基纳米立方体，以实现稳定和选择性的电还原该提案的中心假设有两个：i）将铜基纳米立方体与合理设计的合成聚合物结合起来，以防止电还原过程中颗粒间聚结和表面腐蚀；ii）疏水性聚合物配体控制纳米立方体的微环境并提高纳米立方体的选择性，以N-杂环卡宾（NHCs）封端的聚合物配体将通过稳定的NHC-Cu键锚定在Cu、氮化铜（Cu3N）和核壳Cu/Cu3N纳米立方体上。这些纳米立方体具有最大（100）表面暴露，可有效促进 C-C 偶联并形成聚合物 NHC 配体，从而平衡局部。通过控制聚合物链长和疏水性，在纳米立方体表面附近实现质子催化质子辅助 CO2 还原成 C-C 偶联产物的浓度最大化，并最大限度地减少质子还原反应。将使用原位光谱学和显微镜来探测 Cu3N 纳米立方体，对聚合物链长度相关的扩散特性进行定量测量，并将其与 Cu 和 Cu3N 的催化性能相关联。活性高效聚合物 NHC-Cu 纳米立方体的成功示范反映了 CO2 电还原还允许更广泛地谈判所有其他阴极纳米催化剂的长期稳定性问题，以提高电还原的可持续性。该奖项是 NSF 的法定使命，并已被授予。通过使用基金会的智力优点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

Recent advances in CO 2 capture and reduction

CO 2 捕获和还原的最新进展

• DOI: 10.1039/d2nr02894h
• 发表时间: 2022-08
• 期刊: Nanoscale
• 影响因子: 6.7
• 作者: Wei, Kecheng;Guan, Huanqin;Luo, Qiang;He, Jie;Sun, Shouheng
• 通讯作者: Sun, Shouheng

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO 2 to CO

用于高效选择性电催化将CO 2 还原为CO 的杂配金氢化物纳米团簇

• DOI: 10.1021/jacs.2c00725
• 发表时间: 2022-03
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Gao, Ze;Wei, Kecheng;Wu, Tao;Dong, Jia;Jiang, De;Sun, Shouheng;Wang, Lai
• 通讯作者: Wang, Lai