Tailoring Second Coordination Sphere for Tunable Solid‐Liquid Interfacial Charge Transfer toward Enhanced Photoelectrochemical H2 Production

The recombination of photogenerated charge carriers severely limits the performance of photoelectrochemical (PEC) H2 production. Here, we demonstrate that this limitation can be overcome by optimizing the charge transfer dynamics at the solid‐liquid interface via molecular catalyst design. Specifically, the surface of a p‐Si photocathode is modulated using molecular catalysts with different metal atoms and organic ligands to improve H2 production performance. Co(pda‐SO3H)2 is identified as an efficient and durable catalyst for H2 production through the rational design of metal centers and first/second coordination spheres. The modulation with Co(pda‐SO3H)2, which contains an electron‐withdrawing ‐SO3H group in the second coordination sphere, elevates the flat‐band potential of the polished p‐Si photocathode and nanoporous p‐Si photocathode by 81 mV and 124 mV, respectively, leading to the maximized energy band bending and the minimized interfacial carrier transport resistance. Consequently, both the two photocathodes achieve the Faradaic efficiency of more than 95% for H2 production, which is well maintained during 18 h and 21h reaction, respectively. This work highlights that the band‐edge engineering by molecular catalysts could be an important design consideration for semiconductor‐catalyst hybrids toward PEC H2 production.