Static Organic p‐n Junctions in Photoelectrodes for Solar Ammonia Production with 86% Internal Quantum Efficiency

For photoelectrocatalytic cells, a limitation exists in finding appropriate photoelectrode configurations that couple efficient extraction of high-energy electrons from absorbed photons and selective catalysis. Here we report an organic p-n junction approach to fabricate molecular photoelectrodes for conversion of solar energy and nitrate into valuable ammonia product. Solar irradiation of the photoelectrode generates charge-separated states with electrons and holes spatially separated at the n-type and p-type components, as revealed by surface photovoltage mapping, at a quantum yield of 90%. The high-flux photogenerated electrons are rapidly transferred to the catalyst for solar ammonia production from nitrate reduction at an external quantum efficiency (EQE) and an internal quantum efficiency (IQE) of 57% and 86%, respectively. Time-resolved spectroscopic studies reveal that the large IQE originates from the combined high efficiencies for photoelectron generation, catalyst activation and dark catalysis. In a flow-cell setup coupled with a silicon solar cell, the photoelectrode without bias generates photocurrent of 57 mA cm-2 and ammonia at an EQE of 52%.