Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO2 Photoreduction

Abstract The objective of photocatalytic CO 2 reduction (PCR) is to achieve high selectivity for a single energy‐bearing product with high efficiency and stability. The bulk configuration usually determines charge carrier kinetics, whereas surface atomic arrangement defines the PCR thermodynamic pathway. Concurrent engineering of bulk and surface structures is therefore crucial for achieving the goal of PCR. Herein, an ultrastable and highly selective PCR using homogeneously doped BiOCl nanosheets synthesized via an inventive molten strategy is presented. With B 2 O 3 as both the molten salt and doping precursor, this new doping approach ensures boron (B) doping from the surface into the bulk with dual functionalities. Bulk B doping mitigates strong excitonic effects confined in 2D BiOCl by significantly reducing exciton binding energies, whereas surface‐doped B atoms reconstruct the BiOCl surface by extracting lattice hydroxyl groups, resulting in intimate B‐oxygen vacancy (B‐OV) associates. These exclusive B‐OV associates enable spontaneous CO 2 activation, suppress competitive hydrogen evolution and promote the proton‐coupled electron transfer step by stabilizing *COOH for selective CO generation. As a result, the homogeneous B‐doped BiOCl nanosheets exhibit 98% selectivity for CO 2 ‐to‐CO reduction under visible light, with an impressive rate of 83.64 µmol g −1 h −1 and ultrastability for long‐term testing of 120 h.