Peptide-Guided Metal-Organic Frameworks Spatial Assembly Sustain Long-Lived Charge-Separated State to Improve Photocatalytic Performance.

The controlled fabrication of spatial architectures using metal-organic framework (MOF)-based particles offers opportunities for enhancing photocatalytic performances. The understanding of the contribution of assembly to a precise photocatalytic mechanism, particularly from the perspective of charge separation and extraction dynamics, still poses challenges. The present report presents a facile approach for the spatial assembly of zinc imidazolate MOF (ZIF-8), guided by β-turn peptides (SAZH). We investigated the dynamics of photoinduced carriers using transient absorption spectroscopy. The presence of a long-lived internal charge-separated state in SAZH confirms its role as an intersystem crossing state. The formation of an assembly interface facilitates efficient electron transfer from SAZH to O 2 , resulting in approximately 2.6 and 2 times higher concentrations of superoxide (·O 2 - ) and hydrogen peroxide (H 2 O 2 ), respectively, compared to those achieved with ZIF-8. The medical dressing fabricated from SAZH demonstrated exceptional biocompatibility and exhibited an outstanding performance in promoting wound restoration. It rapidly achieved hemostasis during the bleeding phase, followed by a nearly 100% photocatalytic killing efficiency against the infected site during the subsequent inflammatory phase. Our findings reveal a pivotal dynamic mechanism underlying the photocatalytic activity of control-assembled ZIF-8, providing valuable guidelines for the design of highly efficient MOF photocatalysts.