Hydride-containing 2-Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution
Rhone P Brocha Silalahi1, Yongsung Jo2, Jian-Hong Liao1
1Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd. Shoufeng, Hualien, 97401, Taiwan R. O. C.
Angewandte Chemie (International Ed. in English)
|February 22, 2023
Summary
The first 2-electron palladium/copper alloys containing hydride were synthesized. PdHCu11 exhibits excellent hydrogen evolution reaction (HER) activity, suggesting accessible palladium sites are key for catalyst design.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Catalysis
Background:
- Developing efficient electrocatalysts for the hydrogen evolution reaction (HER) is crucial for sustainable energy technologies.
- Metal nanoclusters offer tunable properties but often lack stability and high activity.
Purpose of the Study:
- To synthesize and characterize novel hydride-containing palladium/copper bimetallic nanoclusters.
- To investigate the hydrogen evolution reaction (HER) activity of these new materials.
Main Methods:
- Synthesis of palladium/copper nanoclusters from a precursor cluster using trifluoroacetic acid (TFA).
- Structural characterization using X-ray diffraction.
- Computational analysis using Density Functional Theory (DFT).
- Electrochemical evaluation of HER performance in acidic media.
Main Results:
- Successful synthesis of two new 2-electron palladium/copper hydride clusters: PdHCu11 and PdHCu12.
- X-ray diffraction confirmed PdHCu11 and PdHCu12 feature a central PdH unit within a Cu11 cuboctahedron and a Cu12 cuboctahedron, respectively.
- DFT calculations revealed both clusters behave as axially-distorted 2-electron superatoms.
- PdHCu11 demonstrated exceptional HER activity with a low onset potential (-0.05 V), favorable Tafel slope (40 mV/dec), and remarkable stability over 1000 cycles.
Conclusions:
- The synthesized PdHCu11 and PdHCu12 clusters represent the first examples of hydride-containing 2-electron palladium/copper alloys.
- PdHCu11 exhibits unprecedented HER activity among metal nanoclusters, attributed to its accessible central palladium site.
- This work provides valuable insights into structure-activity relationships for designing advanced HER electrocatalysts.
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