设计双功能配体构筑O-Ru-O活性域高效催化乙炔氢氯化反应

The application aims at the problem that our country must fulfill the international convention on mercury emission (Minamata Convention) without economic feasible catalysts for acetylene hydrochlorination. Combining the experiment research and molecular simulation methods, this application is proposed to design the dual functional ligands containing aromatic rings. The O-containing functional groups in the ligand can interact with ruthenium precursors to form the highly dispersed O-Ru-O active domains; the aromatic ring in ligand can perform the electron delocalization, and promote the electron transfer in the system, thus promote the electrophilic addition reaction of acetylene and hydrogen chloride reactants; another functional group in the ligand can bond with the groups on the activated carbon surface to anchor and disperse the active domains; Firstly, the ligands with different structure is designed, and the influence law of ligand structure, the types of functional groups and ruthenium precursors, the surface properties of carrier, and the coordination conditions on the formation of O-Ru-O domains is studied, then the construction method of highly dispersed active domains is obtained. Secondly, the influencing mechanism of the spatial structure, and electron transition, distribution and transmission of O-Ru-O domains is revealed, and the reaction mechanism is obtained, then the micro environment, which is beneficial to the electrophilic addition reaction of acetylene and hydrogen chloride, is constructed and the catalytic efficiency is improved. Finally, the catalyst deactivation mechanism and the catalyst regeneration method are explored to form the high efficiency, long-life catalyst. The research achievements of this application will provide scientific basis and technical support for the clean production of vinyl chloride, and they can also afford reference for the efficient construction of other metal catalyst active domains.

本申请针对我国必须履行国际汞减排公约却没有经济可行的乙炔氢氯化非汞催化剂的难题，拟采用实验研究结合分子模拟的方法，设计含双功能团带芳环的配体，利用其含O功能团与钌前驱体作用形成O-Ru-O活性域，利用芳环发生电子离域，促进体系中电子转移和传递，进而促进反应物乙炔和氯化氢的亲电加成反应；利用其另一功能团与载体上基团成键锚定并分散活性域。首先分子设计不同配体，研究配体结构、功能团、钌前驱体、载体表面性质及配位条件对形成O-Ru-O域的影响规律，获得高分散活性域的构筑方法；其次揭示O-Ru-O域空间结构及电子跃迁、分布与传递的影响机制，获得反应机理，构建有利于反应物亲电加成的微环境，提高催化效率；然后探究催化剂的失活机理，获得再生方法，以形成高效、长寿命催化剂。所获研究成果将为乙炔法氯乙烯的清洁生产提供科学基础与技术支撑，还可为其它金属催化剂活性域的高效构筑提供借鉴。

针对我国必须履行国际汞减排公约却没有经济可行的乙炔氢氯化非汞催化剂的难题，本项目采用实验研究结合分子模拟的方法，通过含杂原子配体构筑了一系列的Ф-Ru-Ф活性域（Ф=O、N、P或S），旨在获得高分散活性域的构筑方法、揭示其催化反应机理和失活机理、获得再生方法，以形成高效、长寿命的绿色经济催化剂。首先采用商品化的含O、N或P的钌配合物作为前驱体制备钌基催化剂，并考察其对乙炔氢氯化反应的影响；然后，设计并选用一系列不同构型的含O、N、P或S杂原子配体与钌前驱体作用构筑了活性域，并制备碳载催化剂用于催化该反应。结果表明：配位杂原子周围结构和基团的变化会引起其周围的电子云密度发生变化，从而影响中心金属原子的电子性质，提高Run+的稳定性，抑制氧化态活性组分的还原；而且Ru配合物的形成锚定、分散了活性组分，配合物中杂原子位点和金属位点分别提高了催化剂对反应物氯化氢和/或乙炔的吸附，因此显著提高了其催化活性和稳定性；DFT模拟结果表明：采用不同方法构筑的钌基催化剂催化反应机理不同；使用硝酸浸泡或氯化氢在线吹扫，可使失活催化剂的活性部分恢复，但稳定性仍有待提高。研究成果为乙炔法氯乙烯的清洁生产提供了一定的科学基础与技术支撑，还可为其他金属催化剂活性域的高效构筑提供有益的借鉴。在ACS Sustainable Chemistry & Engineering、Catalysis Science & Technology、Applied Catalysis A-General、ChemCatChem、Plasma Science and Technology等期刊共发表SCI论文9篇，其中中科院一区或二区论文5篇；申请中国发明专利3项，其中授权1项；获得第五届兵团青年科技论坛征集论文二等奖1项，1人入选兵团中青年科技创新领军人才计划，培养合格硕士研究生4人。