Microstructural optimization and surface cluster-grafting were firstly combined.
Cationic Ag clusters were grafted on the surface of (BiO)2CO3 superstructures.
The Ag clusters-grafted BHS displayed enhanced visible light photocatalysis.
Direct interfacial charge transfer (IFCT) from BHS to Ag clusters was proposed.
The charge transfer process and the dominant reactive species were revealed.
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