Water electrolysis is of interest
as a sustainable way
to produce
clean hydrogen and oxygen fuel and help mitigate the rising problems
of climate change while meeting global energy demands. High-efficiency,
stable, and earth-abundant bifunctional catalysts are needed to enable
more effective electrochemical cells for the hydrogen evolution reaction
(HER) and oxygen evolution reaction (OER). Here, we investigate the
synthesis, composition, performance, and mechanism of multimetal catalysts
serving dual functionality in both OER and HER of water electrolysis.
Through a laser synthesis method, we synthesized heterogeneous catalysts
of nanocrystalline multimetallic alloy pockets embedded within an
amorphous oxide matrix. We evaluated the performance and composition
of a range of mixed transition-metal oxide materials for both OER
and HER, ultimately synthesizing a Cr0.01Fe0.27Co0.34Ni0.38O
x
/C
y
catalyst that has a stable, high-rate, and
competitive overall water splitting performance of 1.76 V at 100 mA
cm–2 in an alkaline medium. Using density functional
theory to gain insight as the active site and mechanism, we propose
that the inclusion of a minor amount of Cr increases the degeneracy
of energetic states that lowers the cost of forming the O 2 p–d
bond and H 1 s–d bond due to the hybridization of s, p, and
d orbitals from Cr. Using a two-electrode water electrolysis cell
with a constant potential of 1.636 V to mimic the setup for fuel production,
we found the catalyst to be stable at 14–15 mA cm–2 for 40 h. This laser synthesis method allowing for facile and rapid
synthesis of complex multimetal systems demonstrates how doping a
Fe, Co, and Ni heterogeneous amorphous/nanocrystalline structure with
small amounts of Cr is important for bifunctional catalytic behavior,
particularly for increasing HER functionality in advancing our understanding
for future electrocatalytic design.