Controlled Synthesis of Transition Metal Phosphide Nanoparticles to Establish Composition-Dependent Trends in Electrocatalytic Activity

Courtney A. Downes, Kurt M. Van Allsburg, Sean A. Tacey, Kinga A. Unocic, Frederick G. Baddour, Daniel A. Ruddy, Nicole J. Libretto, Max M. O'Connor, Carrie A. Farberow, Joshua A. Schaidle, Susan E. Habas

Research output: Contribution to journalArticlepeer-review

20 Scopus Citations


Transition-metal phosphides (TMPs) are versatile materials with tunable electronic and structural properties that have led to exceptional catalytic performances for important energy applications. Identifying predictive relationships between the catalytic performance and key features such as the composition, morphology, and crystalline structure hinges on the ability to independently tune these variables within a TMP system. Here, we have developed a versatile, low-temperature solution synthesis route to alloyed nickel phosphide (Ni1.6M0.4P, where M = Co, Cu, Mo, Pd, Rh, or Ru) nanoparticles (NPs) that retains the structure of the parent Ni2P NPs, allowing investigation of compositional effects on activity without convoluting factors from differences in morphology and crystalline phase. As a measure of the controlled changes introduced within the isostructural series by the second metal, the binary and alloyed ternary TMP NPs supported on carbon at a nominal 5% weight loading were studied as electrocatalysts for the hydrogen evolution reaction (HER). The resultant activity of the electrocatalyst series spanned a 125 mV range in overpotential, and composition-dependent trends were investigated using density functional theory calculations on flat (0001) and corrugated (101¯ 0) Ni1.67M0.33P surfaces. Applying the adsorption free energy of atomic H (GH) as a descriptor for HER activity revealed a facet-dependent volcano-shaped correlation between the overpotential and GH, with the activity trend well represented by the corrugated (101¯ 0) surfaces on which metal-metal bridge sites are available for H adsorption but not the flat (0001) surfaces. The versatility of the rational synthetic methodology allows for the preparation of a wide range of compositionally diverse TMP NPs, enabling the investigation of critical composition-performance relationships for energy applications.

Original languageAmerican English
Pages (from-to)6255-6267
Number of pages13
JournalChemistry of Materials
Issue number14
StatePublished - 2022

Bibliographical note

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

NREL Publication Number

  • NREL/JA-5100-83390


  • density functional theory
  • electrocatalysis
  • hydrogen evolution reaction
  • nanoparticle catalyst
  • transition metal phosphide


Dive into the research topics of 'Controlled Synthesis of Transition Metal Phosphide Nanoparticles to Establish Composition-Dependent Trends in Electrocatalytic Activity'. Together they form a unique fingerprint.

Cite this