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In comparison with the developing nano-carbon catalysts, some small organic molecules are also emerging as catalysts with typical features, however, their working mechanism is still unclear. Here, we synthesized a series of viologen-based heterogeneous catalysts with the same molecular skeleton but different substituent groups through anion exchange engineering. These viologen-based molecules were used as a model catalyst to investigate the underlying structure–function relationship for small molecules-based H2O2 electrosynthesis. Differing from the commonly reported carbon-based electrocatalysts, viologens can produce H2O2 in a synergistic manner, which means that viologens can not only directly catalyze oxygen reduction but also serve as a redox mediator. We found that the ring current and H2O2 selectivity of viologens deliver an increasing trend with the increase of the alkyl chain length of alkyl-substituted viologens and further increase when using benzyl as the substituent group. As a result, a benzyl-substituted viologen (BV) delivers the best electrocatalytic performance among the samples, including the highest H2O2 selectivity of 96.9% at 0.6 V and the largest ring current density of about 13.6 mA·mmol−1. Furthermore, density functional theory (DFT) calculations disclose that the carbon atoms bonded with positively charged N are the active sites and the small highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap of BV is beneficial to the synergistic mechanism for H2O2 production. This work sheds new insight into the efficient H2O2 production in a synergistic manner for small molecules-based electrocatalysts.
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