Engineering Ultrathin C3N4 Quantum Dots on Graphene as a Metal-Free Water Reduction Electrocatalyst

Developing an efficient electrocatalyst with the desired architectural and electronic properties is paramount for water splitting. Here, we apply theoretical calculations to experimental studies to uncover the influence of structure engineering (quantizing and support coupling) on the HER catalytic activity and develop an optimized C 3 N 4 hybrid catalyst. Impressively, the desired atom-thick C 3 N 4 quantum dots on graphene (CNQDs@G) has been successfully obtained and achieves HER performance with low overpotential (110 mV) at 10 mA cm –2, large exchange current density (3.67 μA cm –2 ), and long-term durability, better than those of many metallic catalysts. In combination with the experimental results, DFT calculations also disclose that the HER catalytic activity of CNQDs@G originates from bisynergetic effects: one between G and CNQDs and another between the edge pyridinic-N sites and the molecular sieve structure.