CdS incorporation induced gate-opening in UiO-66-NH2 for photocatalysis

Integrating semiconductors into metal-organic frameworks (MOFs) typically compromises porosity due to pore blockage or coverage. Conversely, we report a CdS/UiO-66-NH 2 composite, achieving a 1.5-fold increase in specific surface area. Through in-situ synthesis, CdS clusters are embedded into the tetrahedral pores of UiO-66-NH 2 . Structural analysis utilizing Rietveld-refined synchrotron X-ray diffraction (SXRD) and density functional theory (DFT) reveals the confined CdS clusters modulate the rotation of organic linkers, synchronously expanding the framework by a guest-induced gate-opening effect. In addition, CdS/UiO-66-NH 2 heterostructure significantly facilitates efficient charge carrier separation. Consequently, the optimized CdS/UiO-66-NH 2 exhibits a more than doubled photocatalytic water splitting rate compared to pristine UiO-66-NH 2 . This work offers molecular-level insights into leveraging structural flexibility for constructing high-efficiency photocatalysts. Defying norms, the integration of CdS with UiO-66-NH₂ metal-organic frameworks (MOFs) achieves a 1.5-fold enhancement in specific surface area (SSA) through guest-induced gating-opening effects. This novel CdS/UiO-66-NH 2 composite shows improved photocatalytic water splitting performance. • A guest-induced gate-opening effect in CdS/UiO-66-NH 2 increases specific surface area by 1.5-fold. • Synchrotron XRD and DFT reveal that CdS clusters in tetrahedral pores induce a ~ 26 o linker rotation via Cd N bonding, and expand porosity. • The CdS/UiO-66-NH 2 composite achieves a > 200% enhancement in photocatalytic water splitting rate via increased active site accessibility and improved charge carrier dynamics.