Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst
Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst
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DOI：
10.1021/acssuschemeng.8b05703
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发表时间：
2019-04-01
影响因子：
8.4
通讯作者：
Dinca, Mircea
中科院分区：
文献类型：
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作者：
Metzger, Eric D.;Comito, Robert J.;Dinca, Mircea
金属有机骨架(MOF)作为结构可调的固体催化剂具有很大的应用前景，但其相对较高的成本和有限的稳定性仍然是其作为多相催化剂商业化的重要问题。在这里，我们报道了一类高选择性的烯烃改质MOF催化剂Co-和Ni-mfu-4L的X射线吸收光谱研究，并揭示了它们的失活机理。我们进一步表明，Ni-CFA-1是一种比Ni-MFU-4L更具可扩展性和经济性的替代物，它在乙烯二聚催化中再现了后者的局部配位结构和高选择性。在最佳条件下，经MMAO-12活化的Ni-CFA-1催化剂的转化频率为每小时37100次，1-丁烯的选择性为87.1%，这是多相乙烯二聚催化剂所无法比拟的。Ni-CFA-1在一升半间歇反应器中保持其高活性至少12小时，为工业催化提供了一种稳健和可扩展的MOF的策略。
Metal organic frameworks (MOFs) hold great promise as structurally tunable catalysts capable of high selectivity in the solid state, yet their comparatively high cost and often limited stability remain significant concerns for their commercialization as heterogeneous catalysts. Here, we report detailed X-ray absorption spectroscopy studies of Co-and Ni-MFU-4l, a class of highly selective MOF catalysts for olefin upgrading, and reveal mechanisms that lead to their deactivation. We further show that Ni-CFA-1, a more scalable and economical alternative to Ni-MFU-4l, reproduces both the local coordination structure and the high selectivity of the latter in ethylene dimerization catalysis. Under optimal conditions, Ni-CFA-1 activated by MMAO-12 achieves a turnover frequency of 37100 per hour and a selectivity of 87.1% for 1-butene, a combination of activity, selectivity, and affordability that is unmatched among heterogeneous ethylene dimerization catalysts. Ni-CFA-1 retains its high activity for at least 12 h in a one-liter semibatch reactor, offering a strategy toward robust and scalable MOFs for industrial catalysis.