Harnessing and storing visible light using a heterojunction of WO3 and CdS for sunlight-free catalysis.

CdS and WO3 (CdS/WO3) bilayer film electrodes are fabricated to harness solar visible light (λ > 420 nm) and store photogenerated electrons for possible use during periods of unavailable sunlight. The overall film thickness is approximately 50-60 μm, while the CdS underlayer is slightly thinner than WO3 owing to a packing effect. The energetics of CdS and WO3 determined by optical and electrochemical analyses enables cascaded electron transfer from CdS to WO3. The open circuit potential (EOCP) of CdS/WO3 under visible light (approximately -0.35 V vs. SCE) is nearly maintained even in the absence of light, with a marginal decrease (∼0.15 V) in ∼20 h of darkness. Neither CdS nor WO3 alone exhibits such behavior. The electron lifetimes (τ) of CdS and WO3 are each less than 100 s, whereas coupling of the two increases τ to ∼2500 s at the EOCP. In the absence of dissolved O2, τ further increases, suggesting that O2 is the primary electron acceptor. In spite of oxic conditions, CdS/WO3 is capable of continuously reducing Cr(6+) to Cr(3+) and Ag(+) to Ag(0) after removal of visible light. The number of utilized (i.e., stored) electrons in the reductions of Cr(6+) and Ag(+) are estimated to be ∼1.08 × 10(17) and ∼0.87 × 10(17), respectively. The primary role of CdS is to be a visible-light absorber in the 420-565 nm wavelength range, transferring the photogenerated electrons to WO3. The electrons stored in WO3 are gradually released to electron acceptors with suitable redox potentials.