Spin-state engineering of single-atom cobalt catalysts via carbon nanotube supports enhances catalytic activity

Spin-state plays a crucial role in defining the electronic structure and catalytic reactivity of transition metal catalysts. However, precise manipulation of spin states is challenging, and their impact on catalytic mechanisms remains poorly understood. Here, we show that the curvature of carbon nanotubes (CNTs) tunes the spin state of cobalt phthalocyanine (CoPc) anchored on CNTs, thereby affecting the activity and selectivity in the electroreduction of nitric oxide (NORR) to ammonia. As the CNT diameter falls below 3 nm, the Co2+ center spontaneously transitions from a low-spin (LS) to a high-spin (HS) state. Density functional theory calculations and in situ spectroscopic measurements show that the HS state weakens the N=O bond and promotes bent *NO, which favors NH3 generation. As a result, the optimized catalyst achieves a high partial current density with a Faradaic efficiency of >90% at −0.5 V versus the reversible hydrogen electrode (RHE), while maintaining good stability. This work highlights spin-state engineering via support curvature for selective electrochemical transformations. Nitric oxide electroreduction enables simultaneous pollutant removal and ammonia synthesis, but controlling catalyst spin states is challenging. Here, the authors report carbon nanotube curvature tunes cobalt phthalocyanine spin states, promoting bent NO formation and selective ammonia production.