Title: Facile Synthesis of bimetallic Pt-Pd symmetry-broken concave nanocubes and their enhanced

activity toward oxygen reduction reaction.

Authors: Rifeng Wu, Panagiotis Tsiakaras, Pei Kang Shen

doi: https://doi.org/10.1016/j.apeatb.2019.03.045.

Journal Name: Applied Catalysis B: Environmental

With the excessive consumption of fossil fuels and the resultant environmental damage which includes
the excessive release of CO2 to the atmosphere, increase in global average temperature, etc. mankind
had been forced to shift its perspective to the development of green sustainable energy storage and
conversion devices. The best alternatives to these are the Fuel Cells owing to their high efficiency,
unlimited renewable sources of reactants, zero-emission, and environmental compatibility.

To make Fuel cells economically viable, we have to par the sluggish cathodic Oxygen Reduction Reaction
(ORR), as its contribution to the overpotential is much larger than that of anodic Hydrogen Oxidation
Reaction (HOR). To lower the same, catalysts are required and Pt/C is the state-of-the-art catalyst now
for PEMFCs.

However, Pt being a precious metal is costly, less abundant, and shows less tolerance to contamination
which leads to a major disadvantage. One way to enhance stability and durability is via alloying Pt with
non-transition metals. The activity enhancement of these has been attributed to compressive strain due
to shorter Pt-Pt bond distances and downshifting of the d-band center of Pt due to the ligand effect.

With these insights, this group has prepared Pt-Pd alloy. Apart from this, the morphology and shape of
catalysts also matter. They have prepared a symmetry-broken concave nanocube owing to the fact that
facets and vertexes help in enhancing the catalytic activity.

A one-step synthesis method which includes Pt, Pd precursors along with DMF, PVP, and NaI was
ultrasonicated and heated in an autoclave. Further, they dispersed the nanostructures in Vulcan Carbon
as a support material.

The group had done an in-depth investigation of how every reactant affects the formation of nanocubes.
Firstly, they studied the role of halides by replacing I- with other halides like Br -, Cl-, and in the absence
of I-. It is hard to reduce Pd2+ before Pt4+ due to the lesser reduction potential of Pd 2+/Pd compared to
Pt4+/Pt as a result of which we add iodide ions which will preferentially aid in the reduction of Pd.

Thus, in the absence of I-, an octahedral Pt-Pd nanostructure with uniform distribution is obtained. But,
in the presence of I-, a Pt-rich Pd core-shell was obtained. On replacing with Br -, few irregular
nanoparticles were owing to the effect of Br - as a good capping agent. With Cl-, we again obtained an
octahedral morphology along with irregular nanoparticles. These effects validate the rate of
chemisorption of halide ions on the metal surface i.e. I ->Br->Cl-. Fixing the anion, they tried to assess the
effect of the amount of catalyst by increasing/decreasing NaI, and only slight changes were observed.

They also checked the anion effect in the precursor salt by replacing Cl - with acetylacetonate (acac), and
observed only a size difference from 16.6 nm with Cl - to 5.2nm with acac, thereby stating the fact that
regardless of whether the precursor is Cl-/acac, it does not matter much.
For the synthesis route, they gave a temperature of around 130 oC for 5h. To understand the growth
mechanism, they carried the same reaction for 60 min and 3h at the same temperature. At 60min,
nanocubes of length 8.9nm with an atomic ratio of Pt/Pd to 17.7/55.3 was obtained. While at 3h,
symmetry-broken concave nanocubes were obtained with an edge length of 13.8nm and a Pt/Pd ratio to
be 28.7/71.8. When the reaction was increased to 5h, well-defined Pt-Pd symmetry broken concave
nanocube was obtained with an edge length of 16.6nm with a Pt/Pd ratio of 32.4/97.6. Also, the role of
PVP was done by synthesizing the nanocubes in the absence of PVP, showing an aggregated structure
without specific morphology. On the basis of all the analysis, it was explained that at the initial
nucleation stage, Pd nucleates and grows before Pt to form a thermodynamically stable seed.

The morphological characterization of the sample was explored via TEM which prevents a symmetry-
broken concave nanocube (SBCNC) with an edge length of 16.6nm. Through the HRTEM of a single Pt-Pd
SBCNS, they observed atomic steps and terraces along the concaves of the edge which are enclosed by
(100) and (110) facets. EDS line scan showed that Pd is mainly distributed in the core with the external
surface enriched by Pt with Pt: Pd ratio = 32.4:67.6 as seen by EDS. XRD patterns showed diffraction
peaks at 2θ = 39.9o, 46.2o, 67.8o corresponding to (111), (200), (220) planes of fcc crystalline Pt. The XRD
patterns are shifted to higher angles depicting the formation of Pt-Pd alloy.

To determine the surface chemical state, XPS was conducted which red shift then the negative charge
transfer from Pd to Pt. Further, the ORR behavior was evaluated using RDE by benchmarking against a
46.7% Pt/C catalyst. The Pt reduction peak. Cyclic voltammograms (CVs) were taken for both catalysts in
an N2-saturated 0.1M HClO4 solution. There was a clear positive shift of the Pt-O reduction for the Pt-Pd
SBCNC catalyst compared to the standard Pt/C catalyst. Further, Linear Sweep voltammetry was taken at
different rotating speeds and the mass activity (MA), as well as specific activity (SA), was evaluated. The
Pt-Pd SBCNC exhibited an MA of 0.87 A/mg and SA of 1.93 mA/cm 2 which are 6.2 and 7.7 fold more than
the Pt/C catalyst.

In summary, they have reported a facile and cost-effective Pt-Pd SBCNC catalyst in the one-pot method.
They have also been shown to have superior catalytic activity and long-term durability compared to
state-of-the-art Pt/C catalyst. This paper has exclusively shown the effect of temperature as well as the
choice of reagent on the final product. Creating a synergy between Pt and Pd along with high index
facets they have shown ways to enhance the property of Pt catalyst without adding high cost. Since the
experiment was conducted in an acidic media, they have tried to recreate the fuel cell conditions in
PEMFC. One of the disadvantages of this paper would be the use of Nafion solution in the preparation of
a stable ink. Despite Nafion being highly conductive and feasible for H+ movement, they mask the
electrode material while assessment. A study could be done without the use of Nafion also.

Otherwise, the work produces us with an alternative strategy for designing a catalyst with a simple
route, lower costs, and enhanced catalytic activity and durability towards ORR.