In Situ Design of Metal‐Phenolic Networks Coated Layered Double Hydroxides S‐Scheme Photothermal Nanoreactor for Highly Efficient CO₂ Reduction

Abstract Light‐driven conversion of CO 2 to fuel is the most attractive approach to achieve global carbon neutrality. However, the severe recombination of photogenerated carriers and the narrow range of solar spectrum utilization make its application still challenging. Here, a metal‐phenolic networks (MPNs) coated layered double hydroxide S‐scheme photothermal nanoreactor (CoAl‐LDH @ TA‐Cu‐6 nm) is designed. It can efficiently capture infrared light to achieve a surprising 23‐fold performance improvement over CoAl‐LDH under the simulated sunlight illumination. A variety of in situ characterizations (in situ XPS and DRIFTS) and DFT calculations explore that the fascinating performance comes from the efficient charge separation and migration of the S‐scheme catalysts, the photothermal properties endowed by the creatively introduced MPNs and the nanoscale pseudo‐greenhouse effect brought about by the ingenious coating structure. This work provides new insights into the integration of nanoscale micromorphology and electronic state modification (defect and heterojunction engineering) to achieve broad spectrally responsive photocatalytic nanoreactor design and reveals mechanism for synergistically enhancing photocatalytic activity at the nano‐, atomic‐, and subatomic‐scales, giving a golden key to address the energy crisis and environmental challenges.