Holey carbon nanomeshes with atomically Cu–N4 active sites for efficient carbonyl sulfide catalytic hydrolysis

Abstract

Efficient catalytic hydrolysis of carbonyl sulfide (COS) into easy-to-handle products is crucial for mitigating energy and environmental issues. However, currently investigated catalysts are face the inherent problems of irreversible sulfation and carbonization during the catalytic reaction, making them limit in industrial application. Herein, we report a simple and practical method to synthesize isolated Cu–N4 site on holey nitrogen-modified carbon nanomeshes that can intensely resist sulfur poisoning with a good performance in COS hydrolysis. The representative Cu–N4/NC achieves a COS elimination of nearly 100% and a turnover frequency (TOF(Cu)) of 12.9 h−1 at 70 °C. Importantly, Cu–N4/NC exhibits high long-term stability, with no obvious decline of hydrolysis activity in the run of 32 h, outperforming most of the reported catalysts. The isolated Cu center can effectively modulate the adsorption and desorption of sulfur intermediates and thus avoid the sulfur poisoning of catalysts owing to its unique geometric structure and electronic properties. The in situ characterization demonstrates that isolated Cu–N4 site can effectively catalyze the COS hydrolysis via the adsorbed *HSCO2 and *H intermediates. Our discovery provides an opportunity to design highly active and durability COS desulfurization catalysts with potential for industrial application.