Photoelectrochemical (PEC) reduction of CO2 to value-added chemicals is a promising approach to convert solar energy but it is often suffered from sluggish kinetics and photocorrosion at the semiconductor-electrolyte interface.1, 2 In general, there are two requirements for a good performing solar-driven CO2 reduction: i) effective catalysts for a fast surface redox reaction and ii) an effective semiconductor/catalyst interface for rapid charge transfer across interfaces.3 The deposit of a continuous electrocatalyst layer on the photoabsorber surface can reduce kinetic overpotentials for CO evolution reaction (COER) and can enhance the photoelectrode stability. However, the optical obscuration significantly attenuates the magnitude of the incident illumination. Reducing the coverage (f c) of the catalyst on the photoabsorber surface can reduce the optical obscuration but worsen the reaction kinetics. Moreover, the pinch-off effect occurs as the size of the catalyst is small enough to provide a facile path for carriers to transport across interfaces. The PEC CO2 reduction with the utilization of the pinch-off effects could potentially be advantageous to balance the kinetics and the optical absorption. Understanding the trade-offs between the reduction in photocurrent density due to optical obscuration and the decrease in kinetic overpotentials due to improved active area is important in optimizing PEC CO2 reduction devices.To elucidate the effects of the optical performance, interfacial carrier transport, and electrochemical activity for the PEC CO2 reduction, three possible interfacial configurations in PEC were considered in this study: i) Bare p-Si photocathode case. The bare p-Si photocathode immersed in aqueous electrolyte and CO2R occurs at the semiconductor-electrolyte (SC/E) interface; ii) Layered catalyst case. The continuous layer catalyst is deposited on the surface of p-Si photocathode and forms a semiconductor-metal (SC/M) interface; iii) Patterned catalyst case. Producing a patterned catalyst with a low geometric coverage fraction on the surface of p-Si photocathode. The Schottky junctions with a low barrier height formed by the SC/M are surrounded by the Schottky junctions with a high barrier height formed by the SC/E. We developed a multiphysics model based on the finite element method, including electromagnetic wave propagation, charge transport in bulk semiconductor, species transport in the electrolyte, and charge-transfer kinetics of surface redox reactions.The optical performance and electrochemical performance of CO2R reduction were compared in the three cases. Under the bare p-Si case, the saturation photocurrent densities (J sa) and the onset potential (V on) were -13.40 mA/cm2 and -0.80 V vs. RHE at -1 mA/cm2, respectively. Under the layered catalyst case, the J sa and the V on were -0.84 mA/cm2 and -0.50 V vs. RHE at -0.10 mA/cm2, respectively. Under the patterned catalysts case (f c is 0.1 in this case), the J sa is -12.30 mA/cm2 and V on is -0.69 V vs. RHE at -1 mA/cm2. The magnitude of J sa is influenced by the extent of light obscuration and the magnitude of V on is influenced by the photoelectrode activity and the pinch-off effects. The V on for the patterned case is higher than that of the bare p-Si case due to the improved electrode activity combined with the pinch-off effects. In the bare p-Si case and the patterned catalyst case, the CO2 mass transfer limits the CO partial current density (J CO) to further increase due to high J sa while CO2 mass transfer is not the limitation for COER at high overpotentials for the layered catalyst case due to significant light obscuration. The pinch-off effect also increased the applied voltage corresponding to the maximum J CO for the patterned case (-1.21 V vs. RHE) compared to that for the bare p-Si case (-1.35 V vs. RHE) due to the deceased transport resistance of electrons.The influence of different interfacial configurations, solar concentration ratio, different coverage of catalysts, and different sizes of catalysts for optical loss, pinch-off effect, CO2 mass transfer, current distribution at interfaces, and electrochemical performance are discussed in detail for the optimal design photoelectrode. This framework allows us to provide design guidelines for PEC CO2 reduction devices.
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Jan 1, 2024
Changwen Li + 8
Open Access