The photoelectrochemical oxidation of organic molecules into valuable chemicals is a promising technology, but its development is hampered by the poor stability of photoanodic materials in aqueous solutions, low faradaic efficiency, low product selectivity, and a narrow working pH range. Here, we demonstrate the synthesis of value-added aldehydes and carboxylic acids with clean hydrogen (H2) production in water using a photoelectrochemical cell based solely on polymeric carbon nitride (CN) as the photoanode. Isotope labeling measurements and DFT calculations reveal a preferential adsorption of benzyl alcohol and molecular oxygen to the CN layer, enabling fast proton abstraction and oxygen reduction, which leads to the synthesis of an aldehyde at the first step. Further oxidation affords the corresponding acid. The CN photoanode exhibits excellent stability (>40 h) and activity for the oxidation of a wide range of substituted benzyl alcohols with high yield, selectivity (up to 99%), and faradaic efficiency (>90%).
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