Photocatalytic Oxidative Coupling of Ethane to n-Butane Using CO 2 as a Soft Oxidant over NiTi-Layered Double Hydroxide.

Selective conversion of ethane (C 2 H 6 ) to high-value-added chemicals is a very important chemical process, yet it remains challenging owing to the difficulty of ethane activation. Here, a NiTi-layered double hydroxide (NiTi-LDH) photocatalyst is reported for oxidative coupling of ethane to n-butane (n-C 4 H 10 ) by using CO 2 as an oxidant. Remarkably, the as-prepared NiTi-LDH exhibits a high selectivity for n-C 4 H 10 (92.35%) with a production rate of 62.06 µmol g -1 h -1 when the feed gas (CO 2 /C 2 H 6 ) ratio is 2:8. The X-ray absorption fine structure (XAFS) and photoelectron characterizations demonstrate that NiTi-LDH possesses rich vacancies and high electron-hole separation efficiency, which can promote the coupling of C 2 H 6 to n-C 4 H 10 . More importantly, density functional theory (DFT) calculations reveal that ethane is first activated on the oxygen vacancies of the catalyst surface, and the C─C coupling pathway is more favorable than the C─H cleavage to C 2 H 4 or CH 4 , resulting in the high production rate and selectivity for n-C 4 H 10 .