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

Li, Ping; Lian, Hao; Zhang, Yutong; Yi, Li; Yao, Jiahui; Liu, Penghui; Li, Li-Li; Liu, Xinfeng et al. · ACS Nano · 2024

basic_science · Level V

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Abstract

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<sub>2</sub>, resulting in approximately 2.6 and 2 times higher concentrations of superoxide (·O<sub>2</sub><sup>-</sup>) and hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), 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.