Pendant Proton-Relays Systematically Tune the Rate and Selectivity of Electrocatalytic Ammonia Generation in a Fe-Porphyrin Based Metal–Organic Framework

Electrocatalytic nitrite reduction (eNO₂RR) is a promising alternative route to produce ammonia (NH₃). Until now, several molecular catalysts have shown capability to homogeneously reduce nitrite to NH₃, while taking advantage of added secondary-sphere functionalities to direct catalytic performance. Yet, realizing such control over heterogeneous electrocatalytic surfaces remains a challenge. Herein, we demonstrate that heterogenization of a Fe-porphyrin molecular catalyst within a 2D Metal–Organic Framework (MOF), allows efficient eNO₂RR to NH₃. On top of that, installation of pendant proton relaying moieties proximal to the catalytic site, resulted in significant improvement in catalytic activity and selectivity. Notably, systematic manipulation of NH₃ faradaic efficiency (up to 90 %) and partial current (5-fold increase) was achieved by varying the proton relay-to-catalyst molar ratio. Electrochemical and spectroscopic analysis show that the proton relays simultaneously aid in generating and stabilizing of reactive Fe-bound NO intermediate. Thus, this concept offers new molecular tools to tune heterogeneous electrocatalytic systems.