3D Hydrangea‐like InVO 4 /Ti 3 C 2 T x Hierarchical Heterosystem Collaborating with 2D/2D Interface Interaction for Enhanced Photocatalytic CO 2 Reduction

3D hydrangea‐like InVO 4 /Ti 3 C 2 T x heterosystem is fabricated by in‐situ growth of InVO 4 on Ti 3 C 2 T x and on spot self‐assembly. The formation of a hierarchical architecture collaborating with well‐defined 2D/2D interfacial interaction is constructed by optimizing the ratio of Ti 3 C 2 T x incorporated in the formation of InVO 4 . The as‐obtained InVO 4 /Ti 3 C 2 T x presents improved photon trapping capacity and exposure of reactive sites owing to the enhanced BET specific surface areas, and the capture capacity towards CO 2 is strengthened coordinated with the basic feature of Ti 3 C 2 T x . Based on DFT calculations, the electron transfer from InVO 4 to Ti 3 C 2 T x is demonstrated, and the unique 2D/2D interface interaction in InVO 4 /Ti 3 C 2 T x heterosystem efficiently improves the separation of photogenerated charge carriers. As a result, the 3D hierarchical InVO 4 /Ti 3 C 2 T x heterosystem presents 13.83 μmol g −1  h −1 of CO production (3.1‐folds of pristine InVO 4 ) with 92% selectivity and superior stability. The 3D hierarchical design collaborating with 2D/2D interfacial interaction provides a new avenue to develop ideal catalysts for artificial photosynthesis.