LAUSR

The photocatalytic generation of hydrogen peroxide from water and dioxygen (H 2 O + 1/2O 2  → H 2 O 2 , Δ G ° = +117 kJ mol –1 ) under sunlight is a promising strategy for the artificial photosynthesis of a liquid fuel. We had previously found that resorcinol–formaldehyde (RF) resin powders prepared by the base-catalysed high-temperature hydrothermal method act as semiconductor photocatalysts for H 2 O 2 generation. Herein, we report that RF resins prepared by the acid-catalysed high-temperature hydrothermal method (~523 K) using common acids at pH < 4 exhibit enhanced photocatalytic activity. The base- and acid-catalysed methods both produce methylene- and methine-bridged resins consisting of π-conjugated and π-stacked benzenoid–quinoid donor–acceptor resorcinol units. The acidic conditions result in the resins with a lower bandgap (1.7 eV) and higher conductivity because the lower-degree of crosslinking creates a strongly π-stacked architecture. The irradiation of the RF-acid resins with simulated sunlight in water with atmospheric-pressure O 2 generates H 2 O 2 at a solar-to-chemical conversion efficiency of 0.7%, which is the highest efficiency ever reported for powder catalysts used in artificial photosynthesis. Low-bandgap polymers hold great potential for photocatalytic generation of hydrogen peroxide, but increasing catalytic activity remains challenging. Here, a solar-to-chemical conversion efficiency of 0.7 % is reached for a resorcinol-formaldehyde resin powder prepared via acid-catalyzed high-temperature hydrothermal synthesis.