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，康涅狄格大学的何教授和翁教授以及布朗大学的孙教授正在设计用于二氧化碳（CO2）选择性电化学活化的新型杂化材料。该团队将利用合成聚合物来涂覆和保护铜基催化剂，使所得混合材料在CO2电还原中更加坚固和有效，以产生增值的碳氢化合物产品。利用可再生电力将二氧化碳转化为有用的化学产品可能是可持续性的一个重要组成部分。该合作项目将涉及来自两所大学的本科生，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。从这个项目中获得的成果将通过联合会议、课程、本科生研究活动和外联活动传播给理工科学生。PI正在与新英格兰南部地区的当地高中和外展计划合作，以吸引学生进入STEM学习和潜在的职业道路（科学，技术，工程和数学）领域。在化学系化学催化计划的支持下，康涅狄格大学的何教授和翁教授以及布朗大学的孙教授正在研究新的铜-基于纳米立方体功能化与合成聚合物配体朝向稳定和选择性的CO2电还原。该提议的中心假设是双重的：i）将基于Cu的纳米立方体与合理设计的合成聚合物结合以防止电还原期间的颗粒间聚结和表面腐蚀，以及ii）疏水聚合物配体以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（NHC）为端基的聚合物配体可以通过稳定的NHC-Cu键锚定在Cu、氮化铜（Cu 3 N）和核壳结构的Cu/Cu 3 N纳米立方体上。这些纳米立方体具有最大（100）表面暴露以有效地促进C-C偶联并形成C2+烃产物。聚合物NHC配体将通过控制聚合物链长和疏水性来平衡纳米立方体表面附近的局部质子浓度，以实现最大催化质子辅助CO2还原为C-C偶联产物并使质子还原反应最小化。Cu-NHC键的稳定性和聚合物接枝的Cu和Cu 3 N纳米立方体的结构完整性将使用原位光谱和显微镜进行探测。聚合物链长度依赖的扩散性能将被定量测量和相关的Cu和Cu 3 N纳米立方体的催化性能。成功展示用于CO2电还原的活性和高效聚合物NHC-Cu纳米立方体还可以更广泛地解决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。该奖项反映了NSF的法定使命，并通过使用基金会的知识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

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
• 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