甲烷无氧偶联用SA-FLP双活性位耦合催化剂的设计、构筑与性能研究

甲烷的高效定向转化对于发展以天然气/页岩气为原料的新石化路线具有重大意义，其无氧偶联直接制C2烃因工艺简单、碳利用效率高等优点而备受青睐，但该路线因反应温度高及C2烃收率低至今未实现工业化。本项目提出通过创制单原子-受阻路易斯酸碱对(SA-FLP)双活性位耦合催化剂，强化两分子甲烷共同活化及碳氢物种表面偶联，从而提高甲烷转化率和C2烃选择性，达到降低反应温度和提高C2烃收率的目的。催化剂的研发采用“理论预测→实验验证”的新范式，首先基于过渡金属单原子和可还原性氧化物载体对SA-FLP催化剂进行高通量设计和筛选，然后对有限目标进行定向制备和催化性能验证，最后通过理论和实验揭示甲烷无氧偶联的动态机理，建立催化剂构-效关系，并在微观和宏观层次解析反应动力学。最终开发出高效、稳定、抗积碳的SA-FLP催化剂，实现甲烷无氧偶联在中等高温条件下C2烃收率>12%的目标，为其向工业化发展提供理论与技术支撑。

Selective conversion of methane with high efficiency is of great importance to developing new petrochemical processes by using natural gas/shale gas as resources. Non-oxidative coupling of methane (NOCM) to C2 hydrocarbons (abbreviated as C2 hereafter) has received considerable attention due to the advantages of simple process, high carbon efficiency, etc. However, the high reaction temperature and low yield of C2 greatly hinders its industrialization. In this project, we propose to develop single atom-frustrated Lewis pairs (SA-FLP) dual-active-site catalysts to improve the conversion of methane and the selectivity of C2 via enhancing the simultaneous activation of two methane molecules and the surface coupling of hydrocarbon species, for realizing the final goal of reducing the reaction temperature and improving the C2 yield of NOCM. The development of SA-FLP catalysts will follow a novel paradigm of “from theoretical prediction to experimental verification”: i) Carry out high-throughout design and screening of SA-FLP catalysts based on transition metals and reducible oxide supports; ii) Prepare selected SA-FLP catalysts and test their catalytic performance for NOCM; iii) Reveal the dynamic mechanisms of NOCM, establish the structure-function relationship of the catalysts, and analyze the reaction kinetics at the micro- and macro-levels by using combined theoretical and experimental methods. The ultimate goal of this project is to develop a kind of highly efficient, stable and coke-resistant SA-FLP catalysts to achieve the C2 yield of NOCM higher than 12% at medium-high temperature, providing theoretical and technical supports for the industrial development of NOCM.