An All‐in‐One Lignin‐Based Artificial Thylakoid Nanovesicle Via In‐Situ Confined Growth Strategy for High‐Efficient and Selectivity CO ₂ Photoreduction

ABSTRACT Selective CO 2 photoreduction via artificial photocatalysis into high‐value chemical feedstocks such as CO is a productive strategy for remitting environmental problems and energy crises. Nevertheless, photocatalysts generally endure low activity and poor product selectivity due to the low light/CO 2 capture and slow dynamic transfer of photogenerated electrons. Herein, we describe an all‐in‐one lignin‐based artificial thylakoid nanovesicle (AiO‐L‐ATN) using the confined growth strategy of lignin molecules, inspired by the chloroplast's photosynthesis mechanism. Such AiO‐L‐ATN possesses a high CO generation rate of 98.8 μmol g −1 h −1 at normalized active mass with a satisfactory selectivity of 92.1% in a gas‐solid system with H 2 O, exceeding 26 times that of the primary ZnCdS. Besides, introducing carbon nanovesicles significantly improves CO 2 capture performance, narrows the band gap, expands the wavelength range of light absorption, and accelerates the separation of photogenerated electrons. Density functional theory (DFT) calculation reveals that the carbon nanovesicles with various functional groups favor *CO 2 adsorption, *COOH production and conversion, as well as accelerate the dynamic transfer of photogenerated electrons, thereby endowing the outstanding CO 2 reduction rate and CO selectivity of AiO‐L‐ATN. This study not only provides valuable insights into the preparation of highly efficient photocatalysts but also offers novel avenues for CO 2 photoreduction.