Synthesis of bimetallic nanoparticles is a popular approach
in
developing novel electrocatalytic materials. In this work, by wet
chemical protocols, we synthesized the mixed nickel–palladium
nanocomposite on reduced graphene oxide support (Ni–Pd/rGO)
alone with its monometallic analogues Ni/rGO and Pd/rGO as reference
samples. The structure of the three nanocomposites was revealed by
a set of advanced instrumental methods. In Ni/rGO, nickel evenly covers
the rGO support in the form of single ions, chemically bound to the
surface. In Pd/rGO, palladium is in form of nanoparticles with the
size of 3–8 nm. In Ni–Pd/rGO, nickel uniformly covers
the rGO surface, and Pd forms nanoparticles, similar to that in the
monometallic analogues. At the same time, a thin surface layer of
the Pd nanoparticles is enriched by Ni atoms. The nickel-enriched
layer is not continuous, with a gradient of Ni content from the particle
surface toward its center; its thickness does not exceed dimensions
of two to three atomic layers. Only Pd/rGO and Ni–Pd/rGO demonstrated
catalytic activity toward the hydrogen evolution reaction (HER), suggesting
that catalytic properties stem from Pd, not Ni. Ni–Pd/rGO exhibits
a significantly higher electrocatalytic surface area of 2.421 m2/g, compared to 0.278 m2/g for Pd/rGO, which could
be explained by agglomeration of Pd nanoparticles in the latter and
their lower availability to reagents. Both nanocomposites demonstrated
good stability after 1000 cycles. Despite reduced palladium content,
Ni–Pd/rGO demonstrated higher efficiency toward HER with overpotential
of 63 mV compared to 116 mV for Pd/rGO: the catalytic efficiency is
increased simultaneously with reducing the content of precious Pd
by half. These observations can be explained by the alteration of
the surface energy of the particles due to the difference in electronegativity
and the lattice mismatch between the two metals.