Manipulating Photoconduction in Supramolecular Networks for Solar-Driven Nitrate Conversion to Ammonia and Oxygen

For photoelectrodes to be used in practical catalytic applications, challenges exist in achieving the efficient production and transport of photogenerated charge-separated states. Analogous concepts in traditional inorganic photoelectrodes can be applied to their organic-polymer counterparts with improved charge-separation efficiencies. In this work, we develop photoconductive organic networks to form a high-performance photoelectrode for NO3– reduction to NH3. In the integrated network, interfaces between the organic electron-donating photoconductor and electron-accepting catalyst can generate charge carriers efficiently upon illumination, leading to enhanced charge separation for photoelectrocatalysis. The photoelectrode network is capable of converting NO3– to NH3 at an external quantum efficiency of 13%. By coupling with a BiVO4 photoanode in tandem, the system reduces NO3– to NH3 and oxidizes H2O to O2 simultaneously at Faradaic efficiencies of 95–98% with sustained photocurrents and production yields. Investigation of the photoconductive network by steady-state/time-resolved spectroscopies reveals the efficient generation and transport of free charge carriers in the photoelectrode, providing a basis for high photoelectrocatalytic performances.