skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Controlling the 3-D morphology of Ni–Fe-based nanocatalysts for the oxygen evolution reaction
Controlling the 3-D morphology of nanocatalysts is one of the underexplored but important approaches for improving the sluggish kinetics of the oxygen evolution reaction (OER) in water electrolysis. This work reports a scalable, oil-based method based on thermal decomposition of organometallic complexes to yield highly uniform Ni–Fe-based nanocatalysts with a well-defined morphology ( i.e. Ni–Fe core–shell, Ni/Fe alloy, and Fe–Ni core–shell). Transmission electron microscopy reveals their morphology and composition to be NiO x –FeO x /NiO x core-mixed shell, NiO x /FeO x alloy, and FeO x –NiO x core–shell. X-ray techniques resolve the electronic structures of the bulk and are supported by electron energy loss spectroscopy analysis of individual nanoparticles. These results suggest that the crystal structure of Ni is most likely to contain α-Ni(OH) 2 and that the chemical environment of Fe is variable, depending on the morphology of the nanoparticle. The Ni diffusion from the amorphous Ni-based core to the iron oxide shell makes the NiO x –NiO x /FeO x core-mixed shell structure the most active and the most stable nanocatalyst, which outperforms the comparison NiO x /FeO x alloy nanoparticles expected to be active for the OER. This study suggests that the chemical environment of the mixed NiO x /FeO x alloy composition is important to achieve high electrocatalytic activity for the OER and that the 3-D morphology plays a key role in the optimization of the electrocatalytic activity and stability of the nanocatalyst for the OER.  more » « less
Award ID(s):
1703827
PAR ID:
10100019
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
11
Issue:
17
ISSN:
2040-3364
Page Range / eLocation ID:
8170 to 8184
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Nanotechnology)
    Abstract Among the multi-metallic nanocatalysts, Pt-based alloy nanocrystals (NCs) have demonstrated promising performance in fuel cells and water electrolyzers. Herein, we demonstrate a facile colloidal synthesis of monodisperse trimetallic Pt–Fe–Ni alloy NCs through a co-reduction of metal precursors. The as-synthesized ternary NCs exhibit superior mass and specific activities toward oxygen reduction reaction (ORR), which are ∼2.8 and 5.6 times as high as those of the benchmark Pt/C catalyst, respectively. The ORR activity of the carbon-supported Pt–Fe–Ni nanocatalyst is persistently retained after the durability test. Owing to the incorporation of Fe and Ni atoms into the Pt lattice, the as-prepared trimetallic Pt-alloy electrocatalyst also manifestly enhances the electrochemical activity and durability toward the oxygen evolution reaction with a reduced overpotential when compared with that of the benchmark Pt/C (△ η = 0.20 V, at 10 mA cm −2 ). This synthetic strategy paves the way for improving the reactivity for a broad range of electrocatalytic applications. 
    more » « less
  2. ; ; ; ; ; ; ; ; ; ; et al (, Nanoscale)
    Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems. 
    more » « less
  3. ; ; ; ; ; (, Energy & Environmental Science)
    Octahedrally shaped Pt–Ni alloy nanoparticles on carbon supports have demonstrated unprecedented electrocatalytic activity for the oxygen reduction reaction (ORR), sparking interest as catalysts for low-temperature fuel cell cathodes. However, deterioration of the octahedral shape that gives the catalyst its superior activity currently prohibits the use of shaped catalysts in fuel cell devices, while the structural dynamics of the overall catalyst degradation are largely unknown. We investigate the time-resolved degradation pathways of such a Pt–Ni alloy catalyst supported on carbon during cycling and startup/shutdown conditions using an in situ STEM electrochemical liquid cell, which allows us to track changes happening over seconds. Thereby we can precisely correlate the applied electrochemical potential with the microstructural response of the catalyst. We observe changes of the nanocatalysts’ structure, monitor particle motion and coalescence at potentials that corrode carbon, and investigate the dissolution and redeposition processes of the nanocatalyst under working conditions. Carbon support motion, particle motion, and particle coalescence were observed as the main microstructural responses to potential cycling and holds in regimes where carbon corrosion happens. Catalyst motion happened more severely during high potential holds and sudden potential changes than during cyclic potential sweeps, despite carbon corrosion happening during both, as suggested by ex situ DEMS results. During an extremely high potential excursion, the shaped nanoparticles became mobile on the carbon support and agglomerated facet-to-facet within 10 seconds. These experiments suggest that startup/shutdown potential treatments may cause catalyst coarsening on a much shorter time scale than full collapse of the carbon support. Additionally, the varying degrees of attachment of particles on the carbon support indicates that there is a distribution of interaction strengths, which in the future should be optimized for shaped particles. We further track the dissolution of Ni nanoparticles and determine the dissolution rate as a function of time for an individual nanoparticle – which occurs over the course of a few potential cycles for each particle. This study provides new visual understanding of the fundamental structural dynamics of nanocatalysts during fuel cell operation and highlights the need for better catalyst-support anchoring and morphology for allowing these highly active shaped catalysts to become useful in PEM fuel cell applications. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al (, Nature Communications)
    Abstract Fe-containing transition-metal (oxy)hydroxides are highly active oxygen-evolution reaction (OER) electrocatalysts in alkaline media and ubiquitously form across many materials systems. The complexity and dynamics of the Fe sites within the (oxy)hydroxide have slowed understanding of how and where the Fe-based active sites form—information critical for designing catalysts and electrolytes with higher activity and stability. We show that where/how Fe species in the electrolyte incorporate into host Ni or Co (oxy)hydroxides depends on the electrochemical history and structural properties of the host material. Substantially less Fe is incorporated from Fe-spiked electrolyte into Ni (oxy)hydroxide at anodic potentials, past the nominally Ni2+/3+redox wave, compared to during potential cycling. The Fe adsorbed under constant anodic potentials leads to impressively high per-Fe OER turn-over frequency (TOFFe) of ~40 s−1at 350 mV overpotential which we attribute to under-coordinated “surface” Fe. By systematically controlling the concentration of surface Fe, we find TOFFeincreases linearly with the Fe concentration. This suggests a changing OER mechanism with increased Fe concentration, consistent with a mechanism involving cooperative Fe sites in FeOxclusters. 
    more » « less
  5. ; ; ; ; ; ; (, Nanoscale)
    We report that one can gain active control of the electrocatalytic oxygen evolution reaction (OER) on Ni 3 Fe thin films via externally applied strains. The combination of theory and experiments shows that an elastic strain on the surface can tune the OER activity in a predictable way that is consistent with the d-band model. The OER overpotential can be lowered by uniaxial tensions and increased by compressions in a linear manner. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email