Coherently Coupled Frustrated Lewis Pairs in In ₂ O ₃₋ <i> _x </i> Nanoclusters for Selective CO ₂ Photoreduction to CH ₄

Abstract

Abstract Co‐catalysts integration presents unique opportunities to enhance photoactivity, yet selectivity control and mechanistic understanding within multistep reactions remain fundamental challenges hitherto. In this study, a reshaped kinetic landscape is demonstrated over coherently coupled surface frustrated Lewis pairs (FLPs) on carbon nitride matrix, which mediates directed CO 2 ‐to‐CH 4 conversion with a selectivity of 65.3% (electron basis). The hydrogen‐bonded interface fosters intimate electronic coupling, generating built‐in electric fields that facilitate cascade charge transfer processes. Particularly, exceptionally robust FLPs sites were identified within the sub‐nanosized In 2 O 3− x nanoclusters, in contrast to easily deactivated counterparts in oversized crystalline structures. These enduring FLPs sites confer privileged adaptive binding with CO 2 and mutative C1 intermediates. Correlated in situ infrared and mass spectroscopic analyses track the formation of FLPs‐CO 2 adducts and highlight the predominance of formate (HCOO − ) pathway, surpassing competitive CO evolution. This work opens inspiring prospects for exploring multielectron photochemistry and achievable metrics through distinctive FLPs topologies on sub‐nanostructures.