Bridging MgCo‐LDH via ATP to Enhance the Photocatalytic Activity of BiVO ₄ Photoanodes

The rational design of photoelectrodes to mitigate sluggish interfacial charge kinetics is pivotal for efficient photoelectrochemical water splitting. Herein, we report a ternary photoanode constructed by sequentially integrating a magnesium‐cobalt layered double hydroxide (MgCo‐LDH) cocatalyst and attapulgite (ATP) nanorods onto a BiVO 4 semiconductor. The MgCo‐LDH/ATP composite is first synthesized via a facile ball‐milling method and subsequently deposited onto BiVO 4 . ATP, a natural clay mineral with a hierarchical channel structure, functions as an efficient charge transport mediator. Concurrently, the MgCo‐LDH overlayer serves as a hole‐trapping cocatalyst, while the abundant hydroxyl groups on ATP enhance surface hydrophilicity, collectively promoting photogenerated charge separation and migration. The optimized MgCo‐LDH/ATP/BiVO 4 photoanode achieves a photocurrent density of 5.2 mA cm −2 at 1.23 V versus RHE in 0.5 M K 3 BO 3 electrolyte, significantly outperforming pristine BiVO 4 (1.3 mA cm −2 ), ATP/BiVO 4 (3.2 mA cm −2 ), and MgCo‐LDH/BiVO 4 (4.6 mA cm −2 ). This enhancement is attributed to the synergistic effect where ATP establishes directional charge transport pathways, and MgCo‐LDH accelerates surface water oxidation kinetics. This work presents a viable strategy to engineer low‐cost, mineral‐based hybrid materials for high‐performance solar energy conversion applications.