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Photoassisted electrocatalytic (P-EC) water splitting for H2 production has received much attention. Here, we report a metal-free bifunctional photoassisted catalyst of a polyaniline/carbon dots (PANI/CDs) composite for overall water splitting. In a neutral electrolyte, under visible light, the overpotentials of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) for PANI/CDs/NF are reduced by 150 and 65 mV to reach the current densities of 30 and 20 mA cm–2, respectively. In a full water-splitting cell, under visible light, the current density is 13.27 mA cm–2 at 2.0 V, which increases by 62.8% compared with that under the dark conditions (8.15 mA cm–2). The in situ transient photovoltage (TPV) tests were used to study the light-induced effects on half-reactions of water splitting, as well as the charge-transfer kinetic characteristics at the catalyst interface.

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