Combinatorial discovery of oxidative dehydrogenation catalysts within the Mo-V-Nb-O system

Combinatorial methodologies were used for the synthesis and screening of mixed metal oxide heterogeneous catalysts. Primary screening at low reactant conversions at a throughput of greater than 10,000 catalyst compositions per month was performed by using simultaneous MS and photothermal deflection spectroscopy on spatially separated thick film catalysts with ≈200 μg per catalyst prepared by using automated liquid dispensing. Secondary screening under realistic operating conditions was performed at a throughput of greater than 3,000 catalyst compositions per month on ≈50 mg of catalyst in an array of fixed bed microreactors with gas chromatograph detection. The approach was validated by the discovery of catalysts with superior performance to those previously described for the oxidative dehydrogenation of ethane to ethylene. We show the full implementation and integration of combinatorial methodologies for synthesis, screening, discovery, and optimization of multicomponent heterogeneous catalysts.

本研究采用组合化学方法，开展混合金属氧化物非均相催化剂的合成与筛选工作。初筛阶段于低反应物转化率条件下开展，月处理通量超过10000种催化剂配方：通过自动化液体分配技术制备单份负载量约200 μg的空间分隔厚膜催化剂，并对其同步采用质谱（Mass Spectrometry, MS）与光热偏转光谱（photothermal deflection spectroscopy）技术完成检测。复筛阶段则在真实操作工况下进行，月处理通量超过3000种催化剂配方；采用固定床微反应器阵列装填单份约50 mg的催化剂，并通过气相色谱（gas chromatography, GC）检测完成分析。该方法的有效性通过以下发现得以验证：所筛选得到的催化剂性能优于此前已报道的乙烷氧化脱氢制乙烯所用催化剂。本研究完整展示了组合化学方法在多组分非均相催化剂的合成、筛选、发现与优化全流程中的实施与集成应用。