Generation of holes from intra-valence band for enhanced oxidation potentials under visible light

Breaking the trade-off between oxidation potential and spectral response range has been an enduring challenge in the field of photocatalysis. Here, we present a general approach to initiating intra-valence band (intra-VB) hole generation in organic conjugated molecular crystals under visible light irradiation. The electron -deficient precursor with the intrinsically empty side-VB is introduced by Fe 3+ , enabling electron transition from the intra-VB to the sideVB. By studying five typical conjugated photocatalysts, we demonstrate that holes with strong oxidation potentials (up to 3.85 V vs. RHE) are generated under visible light. For PTCDA molecular crystals, the holes from the intra-VB (HOCO-1 b ) couple with carbonyl groups, forming hole -coupled carbonyl sites (-C=O + ) and extending the hole lifetime by 241 times to 84.5 ns. Efficient hole transfer from -C=O + to reactants subsequently initiates oxidation reactions. The high-energy photogenerated holes exhibit scalable oxidation applicability, such as the degradation of organic pollutants in water under natural sunlight.