In
this work, a series of heterostructure Ag@Ag
3
PO
4
/g-C
3
N
4
/NiFe layered double hydroxide
(LDH) nanocomposites were prepared by a combination of an electrostatic
self-assembly and in situ photoreduction method. In this method, positively
charged p-type Ag
3
PO
4
was electrostatically
bonded to the self-assembled negatively charged surface of the n–n-type
g-C
3
N
4
/NiFe (CNLDH) LDH hybrid material with
partial reduction of Ag
+
to metallic Ag nanoparticles (NPs)
by the photogenerated electrons and available surface −OH groups
of LDH under visible light irradiation. The presence of Ag
3
PO
4
as a p-type semiconductor, the surface plasmon resonance
(SPR) effect of metallic Ag NPs, and oxygen vacancies as O
v
-type defects in NiFe LDH could greatly achieve the quasi-type-II
p–n/n–n dual heterojunctions, which was revealed by
the shifted conduction band and valence band potentials in Mott–Schottky
(M–S) analysis. Among all the optimized heterostructures, CNLDHAgP4
could achieve the highest photocatalytic Cr(VI) reduction rate of
97% and phenol oxidation rate of 90% in 2 h. The heterostructure CNLDHAgP4
photocatalyst possesses a unique morphology consisting of cubic phases
of both Ag NPs and Ag
3
PO
4
, which adhered to
the thin and curvy layers of the CNLDH hybrid for smooth electronic
and ionic charge transport. Furthermore, the intimate Schottky barriers
formed at the interface of quasi-type-II p–n/n–n dual
heterojunctions were verified by the photoluminescence, linear sweep
voltammetry, M–S, electrochemical impedance study, high-resolution
transmission electron microscopy, and X-ray photoelectron spectroscopy
studies. The SPR effect of Ag NPs and oxygen vacancies as O
v
-type defect in NiFe LDH can effectively accelerate the threshold
of charge separation and be the main reason for the enhanced activity
achieved by the as-fabricated heterostructure photocatalyst.