State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China.
Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang, Liaoning 110034, P. R. China.
Proc Natl Acad Sci U S A. 2023 Mar 7;120(10):e2206619120. doi: 10.1073/pnas.2206619120. Epub 2023 Feb 27.
Selective oxidation of methane to organic oxygenates over metal-organic frameworks (MOFs) catalysts at low temperature is a challenging topic in the field of C1 chemistry because of the inferior stability of MOFs. Modifying the surface of Cu-BTC via hydrophobic polydimethylsiloxane (PDMS) at 235 °C under vacuum not only can dramatically improve its catalytic cycle stability in a liquid phase but also generate coordinatively unsaturated Cu(I) sites, which significantly enhances the catalytic activity of Cu-BTC catalyst. The results of spectroscopy characterizations and theoretical calculation proved that the coordinatively unsaturated Cu(I) sites made HO dissociative into •OH, which formed Cu(II)-O active species by combining with coordinatively unsaturated Cu(I) sites for activating the C-H bond of methane. The high productivity of C1 oxygenates (CHOH and CHOOH) of 10.67 mmol gh with super high selectivity of 99.6% to C1 oxygenates was achieved over Cu-BTC-P-235 catalyst, and the catalyst possessed excellent reusability.
在 C1 化学领域，通过金属有机骨架（MOFs）催化剂在低温下选择性氧化甲烷生成有机含氧化合物是一个具有挑战性的课题，因为 MOFs 的稳定性较差。在 235°C 真空条件下用疏水性聚二甲基硅氧烷（PDMS）对 Cu-BTC 进行表面修饰，不仅可以显著提高其在液相中的催化循环稳定性，还可以生成配位不饱和的 Cu(I)位，从而显著提高 Cu-BTC 催化剂的催化活性。光谱特征和理论计算的结果证明，配位不饱和的 Cu(I)位使 HO 离解成 •OH，然后与配位不饱和的 Cu(I)位结合形成 Cu(II)-O 活性物种，从而激活甲烷的 C-H 键。在 Cu-BTC-P-235 催化剂上，C1 含氧化合物（CHOH 和 CHOOH）的高时空收率达到 10.67mmol·gh，对 C1 含氧化合物的选择性高达 99.6%，该催化剂具有优异的可重复使用性。
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