Abstract A photocatalyst comprising binary organic polymer dots (Pdots) was prepared. The Pdots were constructed from poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole), as an electron donor, and 1‐3‐(methoxycarbonyl)propyl‐1‐phenyl‐6.6C61, as an electron acceptor. The photocatalyst produces H2O2 in alkaline conditions (1?M KOH) with a production rate of up to 188?mmol?h?1?g?1. The external quantum efficiencies were 30? (5?min) and 14? (75?min) at 450?nm. Furthermore, photo‐oxidation of methanol by Pdots, followed by a disproportionation reaction and an oxidation reaction, produced the high‐value chemical formate. On the basis of various spectroscopic and electrochemical measurements, the photophysical processes of the system were studied in detail and a reaction mechanism was proposed.
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