Conspectus
Proton-exchange membrane fuel cells (PEMFCs)
are highly efficient
energy storage and conversion devices. Thus, the platinum group metal
(PGM)-based catalysts which are the dominant choice for the PEMFCs
have received extensive interest during the past couple of decades.
However, the drawbacks in the existing PGM-based catalysts (i.e.,
high cost, slow kinetics, poor stability, etc.) still limit their
applications in fuel cells. The Pt-based core–shell catalysts
potentially alleviate these issues through the low Pt loading with
the associated low cost and the high corrosion resistance and further
improve the oxygen reduction reaction’s (ORR’s) activity
and stability. This Account focuses on the synthetic strategies, catalytic
mechanisms, factors influencing enhanced ORR performance, and applications
in PEMFCs for the Pt-based core–shell catalysts. We first highlight
the synthetic strategies for Pt-based core–shell catalysts
including the galvanic displacement of an underpotentially deposited
non-noble metal monolayer, thermal annealing, and dealloying methods,
which can be scaled-up to meet the requirements of fuel cell operations.
Subsequently, catalytic mechanisms such as the self-healing mechanism
in the Pt monolayer on Pd core catalysts, the pinning effect of nitrogen
(N) dopants in N-doped PtNi core–shell catalysts, and the ligand
effect of the ordered intermetallic structure in L10-Pt/CoPt
core–shell catalysts and their synergistic effects in N-doped
L10-PtNi catalysts are described in detail. The core–shell
structure in the Pt-based catalysts have two main effects for enhanced
ORR performance: (i) the interaction between Pt shells and core substrates
can tune the electronic state of the surface Pt, thus boosting the
ORR activity and stability, and (ii) the outer Pt shell with modest
thickness can enhance the oxidation and dissolution resistance of
the core, resulting in improved durability. We then review the recent
attempts to optimize the ORR performance of the Pt-based core–shell
catalysts by considering the shape, composition, surface orientation,
and shell thickness. The factors influencing the ORR performance can
be grouped into two categories: the effect of the core and the effect
of the shell. In the former, PtM core–shell catalysts which
use different non-PGM element cores (M) are summarized, and in the
latter, Pt-based core–shell catalysts with different shell
structures and compositions are described. The modifications of the
core and/or shell structure can not only optimize the intermediate-binding
energetics on the Pt surface through tuning the strain of the surface
Pt, which increases the intrinsic activity and stability, but also
offer a significantly decreased catalyst cost. Finally, we discuss
the membrane electrode assembly performance of Pt-based core–shell
catalysts in fuel cell cathodes and evaluate their potential in real
PEMFCs for light-duty and heavy-duty vehicle applications. Even though
some challenges to the activity and lifetime in the fuel cells remain,
the Pt-based c...