Transition metal sulfides have shown high activity for electrocatalytic oxygen evolution reaction (OER).^[1,2] These materials form oxidized surfaces, under these conditions, which can catalyze OER more efficiently than the corresponding metal oxides.^[2,3] The catalytic properties of transition metal sulfides for OER could indicate a general ability to catalyze oxygen atom transfer reactions. However, sulfide materials have not been much explored for thermal oxidative transformations so far. Application of the earth-abundant sulfides in thermal catalysis would be interesting for the development of more sustainable catalytic processes.

We demonstrate the catalytic activity of mesoscale cobalt sulfide (Co₉S₈) for thermal oxygen atom transfer reactivity including both epoxidations and epoxide deoxygenations. Similarly to what has been observed during OER, the Co₉S₈  surface can oxidize and transform in presence of the strong oxidizing agents of the epoxidation reactions. With use of mild oxygen donors, however, we can show that both pristine Co₉S₈ and surface-oxidized Co₉S₈ outperform cobalt oxide in the thermal catalysis of oxygen atom transfers. Our results show the high catalytic potential of pristine cobalt sulfide in thermal oxygen atom transfer reactions.

[1] Meenakshi Chauhan, Kasala Prabhakar Reddy, Chinnakonda S. Gopinath, Sasanka Deka, ACS Catalysis, 2017, 7, 5871−5879.
[2] Jingde Li, Guihua Liu, Jing Fu, Gaopeng Jiang, Dan Luo, Fathy M. Hassan, Jing Zhang, Ya-Ping Deng, Pan Xu, Luis Ricardez-Sandoval, Zhongwei Chen, Journal of Catalysis, 2018, 367, 43-52.
[3] Wei Li, Dehua Xiong, Xuefei Gao, Lifeng Liu, Chemical Communications, 2019, 55, 8744-8763.