Understanding the hydrolysis mechanism of cyanogen chloride on copper and chromium surfaces

Abstract Cyanogen chloride (CNCl) is a highly toxic agent, but there is currently a lack of research on the catalytic hydrolysis reaction of CNCl on metal surfaces. The low efficiency and unclear mechanism of CNCl hydrolysis reaction have hampered the development and enhancement of protective equipment. In this work, we focused on investigating the adsorption behavior and hydrolysis mechanism of CNCl on copper and chromium surfaces through first‐principle methods. Our findings revealed the most stable adsorption configuration of CNCl on metal surfaces and its terminal flipping behavior during the hydrolysis process. Subsequently, we designed and studied a series of CNCl hydrolysis reaction pathways, primarily involving C‐terminal intermediates. Notably, the adsorption energy of CN* displayed strong linear scaling relationships with that of other key reaction intermediates, directly influencing the activity and selectivity of CNCl hydrolysis. By employing the adsorption energy expression based on the intrinsic properties of substrates and adsorbates, we extended them to identify the adsorption energies of various complex reaction intermediates involved in CNCl hydrolysis. This comprehensive understanding of the reaction mechanism on metal surfaces provides a theoretical foundation and innovative perspective for the further exploration of CNCl hydrolysis catalysts.