Unassisted Photoelectrochemical Hydrogen Production Coupled with Selective Glucose Oxidation Using Metal Halide Perovskite Photoanodes

Abstract Photoelectrochemical (PEC) technology offers a direct pathway to convert solar energy into energy carriers (e.g., hydrogen) without the need for solar‐to‐electricity infrastructure. However, scaling PEC systems to industrial levels remains a challenge due to the limited light absorption capabilities of traditional semiconductors and the energy‐intensive oxygen evolution reaction at the photoanode surface. To address these challenges, a novel metal halide perovskite (MHP) photoanode integrated with a CoNiFe layered double hydroxide (LDH) cocatalyst for selective glucose oxidation reaction (GOR) is developed. The CoNiFe LDH/Ni/MHP photoanode achieves a photocurrent density of 24.48 mA cm −2 at 1.23 V versus RHE, with an onset potential of 0.04 V versus RHE for GOR. Prolonged illumination test reveals a 97.3% Faradaic efficiency for gluconic acid production at 0.4 V versus RHE. More importantly, an unbiased, simultaneous PEC H 2 production with GOR (PEC H 2 ‐GOR) system is demonstrated, achieving a stable photocurrent density of 10.1 mA cm −2 . A techno‐economic feasibility assessment highlights the commercialization potential of PEC H 2 ‐GOR technology. This work demonstrates a simultaneous and unassisted hydrogen production and glucose oxidation process over an active and selective MPH‐based photoanode, paving the way for sustainable fuel and chemical photosynthesis.