Promoting C–S Coupling for Hydroxymethanesulfonate Electrosynthesis over Cu-Mn Phthalocyanine Metal–Organic Frameworks

Electrocatalytic C–S coupling to synthesize high-value organosulfur chemicals represents a sustainable paradigm shift from traditional thermochemical processes, yet the electrocatalytic performance remains far from satisfactory. Herein, we develop Cu-Mn bimetallic phthalocyanine metal–organic frameworks (PcCu-Mn) as a highly efficient catalyst for hydroxymethanesulfonate (HMS) synthesis from CO2 and SO32–. When operated in a membrane electrode assembly electrolyzer, PcCu-Mn delivers a record-high HMS yield rate of 285.4 mmol h–1 g–1 and a high Faradaic efficiency of 51.2% along with long-term stability for over 200 h of electrolysis. Mechanistic operando spectroscopic and theoretical investigations reveal the spatial synergy of Cu-Mn dual sites to enable the simultaneous CO2 reduction into electrophilic *CHOH and SO32– activation into nucleophilic *SO3 while promoting *CHOH/*SO3 intermolecular C–S bond formation for selective HMS generation. Furthermore, a comprehensive techno-economic analysis validates the commercial viability of HMS production via the PcCu-Mn-driven electrochemical C–S coupling route.