功能化共价有机框架(COFs)新型材料催化醇脱氢偶联制酯类的研究

Dehydrogenative coupling of alcohols to the related esters is an efficient and eco-friendly reaction process. However, it is deeply limited in the practice due to the low activation performance and poor efficiency of heterogeneous and homogeneous catalysis, respectively. Fortunately, the emerging porous crystals covalent organic frameworks (COFs) have the potential to integrate the advantages of both heter- and homo-geneous catalysts. Based on the in-situ and post-treat methods, in this proposal, we will develop a series of COF-based catalysts, including acid/oxidative bi-functional COF catalysts, COF supported noble or alloy nanoparticle catalysts and organometallic pincer complex immobilized COF catalysts, for the directly dehydrogenative coupling of alcohols to esters by introducing high activated groups or particles into the framework of COFs. In this proposal, we will gain the methodology of the preparation of high performance COF catalyst for the alcohol-ester conversion and the activation mechanism of these new-developed catalysts. It will not only extend the fundamental knowledge of the chemical modification of COF based materials, but also highly match the market's requirement of high efficient catalysts.

醇直接脱氢偶联成酯是一个高效、清洁的反应路径，但是现有的多相催化和均相催化剂分别存在性能和效率上的制约。新近出现的共价有机框架（COFs）多孔晶体具有结合两类催化剂优势的潜力。在本项目中，我们将基于原位合成和后处理手段，将对醇类碳氢键和氢氧键具有优异活化性能的基团/粒子引入到COFs的骨架内，开发包括酸性/氧化性双功能COF催化剂、COF担载贵金属/合金纳米粒子催化剂和有机金属固相化COF催化剂等一系列高效催化剂用于醇直接脱氢偶联。通过本项目，我们将获得醇类脱氢偶联高效COF催化剂的制备方法学和各自的活化机理。本项目不仅有利于拓展和丰富对COF基材料的化学改性的基础认知，而且契合高效催化剂的社会实践需求。

本项目在实施过程中以新型COFs材料的结构调控、功能化、催化位点建立与控制为核心，成功获得一系列COF基新型催化剂，并应用于能源转化与存储过程。本项目支持开展的研究活动已发表SCI文章27篇，包括Nature Commun, Angew Chem Int Ed, ACS Nano, ACS Cent Sci, Carbon Energy和Chem Eng J等IF>10或中科院1区的知名期刊文章15篇。项目实施期间申请发明专利数十项，授权专利15项。本项目相关的专利作为转让标的的一部分成功实现技术转让一项，转让金额360万元。.通过离子化金属有机聚合物(Carbon Energy, (2023), 10.1002/cey2.303)、将二芳胺衍生物整合到共卟啉基框架中（Angew Chem Int Ed, 61 (2022) e202213522）、COF异质双原子固定(Small Structures, 3 (2022) 2100225.)、金属氮配位保护(Small, 18 (2022) e2204757; Chem Commun, 58 (2022) 13214.)、异质框架材料复合(J Mater Chem A, 10 (2022) 228.)等难点的攻克，研发了一系列高效ORR/OER催化剂。通过COF骨架可控碳化(Carbon Energy, (2023) 10.1002/cey2.300.)、高配位非贵金属原子固定(Small, 18 (2022) e2200736.)、氮氧异质配位非贵金属单原子(Chem Eng J, 450 (2022) 138427.）等方面研究研发了多种高效的二氧化碳电还原催化剂。通过框架材料键合方式的固相化创新(Chem Eng J, 441 (2022) 135996.) 、聚合物模板与框架材料可控复合(Nature Commun, 13 (2022) 6673.)、碳骨架材料离子功能化(npj Clean water, 5 (2022) 68.)等研究拓展了该类COF材料在高效吸附、分离、传感等领域的特色应用。