Nanoconfined Nickel@Carbon Core–Shell Cocatalyst Promoting Highly Efficient Visible‐Light Photocatalytic H 2 Production

The realization of large‐scale solar hydrogen (H 2 ) production relies on the development of high‐performance and low‐cost photocatalysts driven by sunlight. Recently, cocatalysts have demonstrated immense potential in enhancing the activity and stability of photocatalysts. Hence, the rational design of highly active and inexpensive cocatalysts is of great significance. Here, a facile method is reported to synthesize Ni@C core–shell nanoparticles as a highly active cocatalyst. After merging Ni@C cocatalyst with CdS nanorod (NR), a tremendously enhanced visible‐light photocatalytic H 2 ‐production performance of 76.1 mmol g −1 h −1 is achieved, accompanied with an outstanding quantum efficiency of 31.2% at 420 nm. The state‐of‐art characterizations (e.g., synchrotron‐based X‐ray absorption near edge structure) and theoretical calculations strongly support the presence of pronounced nanoconfinement effect in Ni@C core–shell nanoparticles, which leads to controlled Ni core size, intimate interfacial contact and rapid charge transfer, optimized electronic structure, and protection against chemical corrosion. Hence, the combination of nanoconfined Ni@C with CdS nanorod leads to significantly improved photocatalytic activity and stability. This work not only for the first time demonstrates the great potential of using highly active and inexpensive Ni@C core–shell structure to replace expensive Pt in photocatalysis but also opens new avenues for synthesizing cocatalyst/photocatalyst hybridized systems with excellent performance by introducing nanoconfinement effect.