二维功能材料构筑及其电催化协同CO2羧化有机合成研究

The catalytic conversion of biomass and derivatives to high-added value chemicals has been the subject of intense research efforts during the past few decades. However, the lack of efficient catalyst and catalytic technology has been the biggest obstacle for high-value utilization of biomass. This project aims to tackle such an important issue by innovative development of negative pressure assisted vapour-phase hydrothermal method to construct nickel-based bimetallic (NiFe, NiCo) MOFs (Metal-Organic Frameworks) thin-layer nanosheet array structures on conductive substrate (e.g., Commercial Carbon Fiber Cloth), followed by the surface functionalization using metallic carbine compounds. Also, another important content of this project is to develop a new electrocatalysis reaction setup with controllable pressure and temperature to systematically study the conversion process and mechanism of furfural to 2,5-furandicarboxylicacid (FDCA) under electrocatalysis conditions. A collective and coherent computation, control synthesis, mechanistic study and performance evaluation methodology will be adopted to facilitate an effective and efficient investigation of these materials systems. The methodology is capable of simply and effectively identifying the key factors affecting the catalytic activities and selectivity, revealing the inherent relationships between the structural, component, surface atomistic, electronic and energetic structure characteristics of catalysts and their catalytic activity and selectivity, predicting the surface atomistic, electronic and energetic properties best matching the high performance catalyst, and providing invaluable information to enable high efficiency targeted control synthesis of high performance furfural conversion catalysts. In mechanism study aspect, the activation of C-H bond in furfural molecule and simultaneously facilitated CO2 carboxylation reaction under electrocatalysis conditions will be systematically investigated, revealing some new mechanisms of electrocatalysis enhanced CO2 carboxylation simultaneously electrocatalysis oxidation on Ni-based bimetallic MOFs catalysts. The success of the project will pave the way to new catalytic reaction technology for greatly improving high-value utilization of biomass source.

本项目以生物质转化平台分子糠醛高效选择性催化转化为2,5-呋喃二甲酸为主要研究目标，创新地使用负压辅助气相水热方法构筑镍基双金属（镍铁、镍钴）MOFs薄层纳米片阵列结构并进一步功能化修饰金属卡宾化合物，发展可加压、加热电催化反应有机合成新工艺，探索电催化条件下糠醛催化转化过程和机制。拟采用理论计算-结构设计-可控合成-机理研究-性能评价的系统研究方法，探索负压辅助气相水热原位生长镍基双金属MOFs薄层纳米片阵列结构最佳条件和电催化条件下镍基双金属MOFs催化剂表面/局域电子、能级结构状态、不饱和过渡金属活性位点等，及其与糠醛催化氧化并同时CO2羧化反应性能的内在关联性及调控规律；揭示生物质转化平台分子糠醛中C-H键在电场/电催化辅助条件下促进其活化并CO2羧化反应新机制，从而获得电催化转化糠醛过程的强化新机制。本项目的成功实施将促进生物质高值化利用技术的发展和应用。

发展常温、常压电催化高值化学品合成技术已经引起广泛关注，其中高效、廉价过渡金属电催化剂的构筑是关键。本项目以生物质转化平台分子糠醛等高效选择性催化转化为高值化学品为主要目标，进一步探索了电催化合成技术用于固氮合成氨、氮氧化物，合成双氧水，以及实现高效C-N偶联合成尿素等。发展了负压辅助气相水热方法构筑了系列镍基双金属（镍铁、镍钴）MOFs薄层纳米片阵列结构电催化剂材料，设计并研制了可加压、加热电催化反应工艺装置，理论结合实验系统地揭示了催化剂材料组成、结构等与其电催化性能的内在关系。具体地，开展的研究内容包括：（1）设计并研制了气相水热反应催化剂材料合成装置，以及系列常温常压电催化反应装置，合成了多种过渡金属MOFs材料并用于电催化合成研究；（2）构筑系列高效电催化剂实现糠醛等有机物加氢、氧化合成高附加值化学品；（3）进一步探索了常温、常压电催化技术固氮合成氨、氮氧化物，氧还原合成双氧水，以及高效C-N 偶联合成尿素等。至项目结题，依托本项目总计发表SCI论文29篇，其中，项目第一标注SCI论文14篇（基金号：51872292）；项目第二标注SCI论文10篇（基金号：51872292）；项目第三标注SCI论文5篇（基金号：51872292）。一些重要科研成果发表在Nat. Sust.、Angew. Chem. Ed. Int.、Adv. Mater.、Appl. Catal. B等国际知名期刊上。依托本项目，获得授权国家发明专利2项，培养博士后1名，博士研究生6名，硕士研究生2名，其中2名博士生分别获得2020年和2022年中国科学院院长优秀奖。本项目对于发展可再生能源驱动的电催化合成技术具有重要意义，部分研发的催化剂产品和电催化反应装置已受到有关公司企业的关注，并与课题组建立了长期研发合作关系，对有关领域的发展起到重要的推动作用。