二氧化碳加氢直接制乙二醇

The conversion of carbon dioxide into fuels and chemicals is an effective solution to reduce carbon emissions and achieve carbon resource utilization, which has become one of the methods for the synthesis of methanol and ethanol. However, the direct synthesis of ethylene glycol by the hydrogenation of carbon dioxide is still a challenging subject in the field of C-1 chemistry. The main challenges are as follows: 1) Easy to form other C1 compounds (such as, methane, methanol, and formic acid); 2) The selective activation of carbon-oxygen bond and then formation of carbon-carbon bond are difficult. In view of the above difficulties, the project plans to develop a moderately active and highly selective catalyst for hydrogenation of carbon dioxide under low temperature and low pressure. In this project, a series of 2D molybdenum sulphide-supported metals catalysts with the characteristics of carbon-oxygen bond activation and carbon-carbon coupling were developed and their catalytic performance for the direct synthesis of ethanol by hydrogenation of carbon dioxide were investigated. To elucidate the structure-performance relationship, the morphology, structure and properties of the Mo2S-based catalysts were systematically analyzed using various characterization techniques. The changes in the structure, coordination environment and electronic structure of catalysts in the reaction process were studied by the in-situ XAFS, MAS NMR and environmental electron microscopy. Combined with theoretical calculation, the active sites and reaction mechanism of the catalytic reaction were investigated at the atomic and molecular level, to realize the directional conversion of carbon dioxide and provide an effective new way for the synthesis of ethylene glycol.

将二氧化碳转化为燃料和化学品是减少碳排放和碳资源化利用有效的解决方法，已成为合成甲醇和乙醇的途径之一，但二氧化碳加氢直接制乙二醇目前仍然是碳一化学领域的挑战性课题。主要困难是：容易形成其它单碳产物（如：甲烷、甲醇及甲酸等）；碳-氧键的选择性活化及进一步碳-碳键的形成较难。针对上述难点，本项目计划开发活性适中且具有高度选择性催化剂，并且控制反应在低温、低压条件下进行。主要研制一种二维硫化钼负载的金属催化剂，从宏观尺度、纳米尺度及原子尺度三重尺度上有效调控催化剂的性能，实现碳-氧键选择性活化和碳-碳偶联的同时控制，达到二氧化碳加氢直接制乙二醇的目的。利用同步辐射、固体核磁、环境电镜等原位动态技术研究催化剂在反应过程中的结构、配位环境和电子结构的变化，并结合理论计算，力争在原子和分子水平上阐明催化反应的活性位和反应机制，以实现二氧化碳的定向转化，为合成乙二醇提供一条有效的新途径。

将二氧化碳转化为燃料和化学品是减少碳排放和碳资源化利用有效的解决方法，已成为合成甲醇和乙醇的途径之一，但二氧化碳加氢直接制乙二醇目前仍然是碳一化学领域的挑战性课题。主要困难是：容易形成其它单碳产物（如：甲烷、甲醇及甲酸等）；碳-氧键的选择性活化及进一步碳-碳键的形成较难。针对上述难点，本项目计划开发活性适中且具有高度选择性催化剂，并且控制反应在低温、低压条件下进行。主要研制一种二维硫化钼负载的金属催化剂，从宏观尺度、纳米尺度及原子尺度三重尺度上有效调控催化剂的性能，实现碳-氧键选择性活化和碳-碳偶联的同时控制，达到二氧化碳加氢直接制乙二醇的目的。利用同步辐射、固体核磁、环境电镜等原位动态技术研究催化剂在反应过程中的结构、配位环境和电子结构的变化，并结合理论计算，力争在原子和分子水平上阐明催化反应的活性位和反应机制，以实现二氧化碳的定向转化，为合成乙二醇提供一条有效的新途径。项目执行期间，项目负责人以第一作者发表了1篇碳一化学前瞻性文章（Chem, 2020, 6, 2496-2514），系统评述了所在团队与国际同行近十年来在碳一分子转化方面的最新进展和重要突破，特别关注了新的催化反应过程，为碳一化学催化新过程、新体系的探索提供了重要借鉴。同时也详细讨论了碳一催化化学的关键挑战及未来发展方向。另外，申请了与本项目相关的专利1件。