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Modulating the Selectivity of H2O2 Activation via Interface Affinity-Dependent Metal-MOF Interactions in Pt-Based
Zhenjiang Liu1, Hailong Chen1,2, Qian Wu1
1School of Environmental and Safety Engineering, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, P. R. China.
None:
Modulating the spatial position of active sites on MOF support offers a promising strategy for selective H2O2 activation. However, the mechanism for regulating the selectivity of key intermediates in H2O2 activation reactions is still unclear. Herein, we design two Pt-based nanozymes by integrating Au@Pt nanoparticles (NPs) into the external surface (Au@Pt/ZIF-8) and the pores (Au@Pt@ZIF-8) of ZIF-8, and systematically study the intrinsic relationship between the spatial position of metal NPs and the selectivity of H2O2 activation. The experimental results indicate that the Au@Pt@ZIF-8 with more Pt-N bonds at the interface exhibits excellent catalytic activity, mainly producing singlet oxygen (1O2), while Au@Pt/ZIF-8 with fewer bonds is mainly dominated by hydroxyl radicals (•OH). Mechanism studies reveal that Au@Pt@ZIF-8 with more Pt-N bonds produces more electron-deficient Pt sites, significantly reducing the energy barrier of the critical step (*OH → *O), and promoting the generation of 1O2. On the contrary, the Pt sites in Au@Pt/ZIF-8 have higher electron density, resulting in a higher energy barrier for the key step, and facilitating the accumulation of *OH. Importantly, a highly sensitive biosensor based on the Au@Pt@ZIF-8 nanozyme is successfully constructed for organophosphorus pesticide detection, with a limit of detection of 1 ng L-1. This work not only elucidates the atomic-level mechanism by which spatial position regulates catalytic behavior via interfacial chemical bonding, but also provides new insights for the rational design of efficient H2O2 activation.
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