含硫缺陷硫化钼高选择性催化CO2制甲醇体系的设计构建及其机理研究

The selective catalytic conversion of carbon-based energy-carrier molecule CO2 to methanol can not only mitigate the anthropogenic CO2 emission, but also realize the utilization of CO2 by means of the methanol economy, which is of great significance for the implementation of our national green circular economy development strategy. Thus far, as for the catalytic conversion reaction of CO2 to methanol, it is highly desirable to improve the efficiency, the selectivity toward methanol and the stability of catalysts. In this context, it is urgent to focus on the design and synthesis of catalysts and control the reaction route so as to explore efficient and stable catalysts with high selectivity for CO2 conversion to methanol. This project will launch an explorative study on the design and preparation of molybdenum sulfide with sulfur vacancies (denoted as MoS2-δ), and their catalytic performances for the selective CO2-methanol conversion. Protocols for the preparation of MoS2-δ with controllable sulfur vacancies will be explored. The influences of sulfur vacancies on the adsorption and activation of reactant molecules (CO2 and H2), and the catalytic reaction mechanism, the structure-activity relationship, the regulative laws for catalytic conversion of CO2 to methanol, and methodologies to regenerate MoS2-δ catalysts will be investigated, with the goals to optimize MoS2-δ based catalysts and improve their efficiency, selectivity and stability for selective CO2 conversion to methanol. It is expected that this project will provide important theoretical basis for developing novel, cost-efficient systems with high performance for effective utilization of CO2.

选择性催化碳基载能分子CO2定向转化为甲醇，既可减少CO2排放，又能利用“甲醇经济”实现CO2资源化利用，对于我国绿色循环经济的发展战略目标有重要意义。针对提高催化还原CO2制甲醇反应效率、选择性、催化材料稳定性的研究需要，亟需从催化材料的设计合成及其对特定反应路径的选择性等科学问题着手，开发高效稳定的催化材料，实现CO2到甲醇的高选择性定向转化。本项目拟设计制备含硫缺陷硫化钼催化剂，并对其热催化加氢还原CO2定向转化为甲醇的性能进行深入探究。探索该类催化材料的可控合成，研究含硫缺陷硫化钼催化剂对反应物分子(CO2、H2)吸附、活化、催化CO2转化为甲醇的作用机制、构效关系和调控规律，探索其催化活性的再生方法，实现对含硫缺陷硫化钼催化体系的优化，提高含硫缺陷硫化钼催化CO2定向转化为甲醇的活性、选择性和稳定性，为建立高效CO2高值利用反应新体系提供重要的理论基础。

构建高效的CO2催化还原体系生产含碳原料或精细化学品为丰富能源供应和减少温室气体排放提供了一种绿色催化转化策略，对于调整我国能源结构、促进经济社会可持续发展具有重要意义。在该项目的支持下，项目组围绕硫化钼基催化材料的可控合成，CO2催化还原体系的构建及性能调控，以及CO2还原反应的催化机理的深入研究等关键问题展开研究工作，取得的主要进展如下：（1）通过光沉积法在半导体光催化剂上负载片状硫化钼构建复合光催化材料，实现了对硫化钼催化材料的可控合成；（2）通过构建异质结构、负载单原子等助催化剂、引入缺陷等策略对半导体材料进行改性，优化光催化CO2还原体系的性能，并通过原位同步辐射等先进表征手段研究CO2还原反应的机理；（3）构建了协同利用光生电子空穴的CO2还原和有机合成耦合反应体系。.在项目执行期间，项目组已在Nature Sustainability, Nature Communications, Journal of the American Chemical Society, Angewandte Chemie, Chemical Reviews, Chemical Society Reviews, ACS Nano, Chemical Science, Nano Today, ACS Catalysis, Applied Catalysis B, Chinese Journal of Catalysis, Nano Research等国内外高水平学术期刊上发表论文53篇，申请中国发明专利5项，目前已授权4项。