Understanding Bridging Sites and Accelerating Quantum Efficiency for Photocatalytic CO(2) Reduction

We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO(2) reduction reaction (CO(2)RR) via Mo–S bridging bonds sites in S(v)–In(2)S(3)@2H–MoTe(2). The X-ray absorption near-edge structure shows that the formation of S(v)–In(2)S(3)@2H–MoTe(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface. The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption, time-resolved, and in situ diffuse reflectance–Infrared Fourier transform spectroscopy. A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S(v)–In(2)S(3)@2H–MoTe(2)(5) photogenerated carrier concentration relative to pristine S(v)–In(2)S(3). Benefiting from lower carrier transport activation energy, an internal quantum efficiency of 94.01% at 380 nm was used for photocatalytic CO(2)RR. This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO(2)RR. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-023-01221-3.