In Situ Evolution of Ru4Al13 Crystals into a Highly Active Catalyst for the Hydrogen Evolution Reaction

  • Kriti Seth
    Kriti Seth
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    More by Kriti Seth
  • Albert J. Darling
    Albert J. Darling
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
  • Cameron F. Holder
    Cameron F. Holder
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
  • Yihuang Xiong
    Yihuang Xiong
    Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
  • Jeffrey R. Shallenberger
    Jeffrey R. Shallenberger
    Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
  • , and 
  • Raymond E. Schaak*
    Raymond E. Schaak
    Department of Chemistry,  Materials Research Institute,  Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    *Email: [email protected]
Cite this: Chem. Mater. 2021, 33, 17, 7124–7131
Publication Date (Web):August 20, 2021
https://doi.org/10.1021/acs.chemmater.1c02583
Copyright © 2021 American Chemical Society
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Abstract

Materials that catalyze the hydrogen evolution reaction (HER) are important for producing H2 as a zero-emission fuel. Ru-based materials are becoming increasingly studied as HER catalysts because they often perform comparably to Pt, the benchmark for this reaction. Despite the availability of a growing number of high surface area Ru-based HER catalysts, these materials can be challenging to synthesize. In contrast, bulk Ru-based materials can be readily synthesized by using established solid-state chemistry techniques. While bulk compounds are undesirable as practical catalysts because of their low surface areas, they allow candidate catalysts that are not yet accessible as high surface area materials to be evaluated and studied. Using this approach for Ru-based materials, we show here that the surfaces of millimeter-scale single crystals of the intermetallic compound Ru4Al13 become rough, pitted, and enriched in Ru, consistent with computed Pourbaix diagrams, upon exposure to acid due to selective Al leaching. The resulting material, having a Ru-rich Ru–Al surface and a Ru4Al13 core, catalyzes the HER in 0.5 M H2SO4 with overpotentials of 18 and 39 mV at current densities of −10 and −100 mA/cm2, respectively, when normalized to geometric surface areas. These values are comparable to higher surface area nanoparticle catalysts, including Pt. This in situ acid-mediated evolution of a bulk crystal into a surface-roughened derivative demonstrates a pathway for engineering catalytic materials that can be readily made as bulk crystals but not yet as higher surface area nanostructures.

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  • Additional images of the Ru4Al13 crystals and electrodes, electrode conditioning data, XRD data for Pt nanoparticles, polarization and chronopotentiometry data, dissolution data, SEM and EDS data, Pourbaix diagrams, and XPS data (PDF)

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