Hybridization
of homogeneous catalytic sites with a photoelectrode
is an attractive approach to highly selective and tunable photocatalysis
using heterogeneous platforms. However, weak and unclear surface chemistry
often leads to the dissociation and irregular orientation of catalytic
centers, restricting long-term usability with high selectivity. Well-defined
and robust ligands that can persist under harsh photocatalytic conditions
are essential for the success of hybrid-type photocatalysis. Here,
we introduce N-heterocyclic carbene as a durable linker for the immobilization
of a Rubpy complex-based CO2 reduction site (cis-dichloro-(4,4′-diphosphonato-Rubpy)(p-cymene)
(RuCY)) on a p-type gallium nitride/gold nanoparticle (p-GaN/AuNP)
heterostructure. The p-GaN/AuNPs/RuCY photocathode was coupled with
a hematite photoanode to drive photoelectrochemical CO2 reduction along with water oxidation. Highly selective CO2 reduction into formates, up to 98.2%, was achieved utilizing plasmonic
hot electrons accumulated on AuNPs. The turnover frequency was 1.46
min–1 with a faradic efficiency of 96.8% under visible
light illumination (243 mW·cm–2). This work
demonstrates that the N-heterocyclic carbene-mediated surface functionalization
with homogeneous catalytic sites is a promising approach to increase
the sustainability and usability of hybrid catalysts.
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