Abstract
Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm2 (AM1.5G, 100 mW/cm2) at a potential of 0 V vs. RHE (j0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j0 of -2.14 mA/cm2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. We believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.