Effects of Metal-Doping on Hydrogen Evolution Reaction Catalyzed by MAu₂₄ and M₂Au₃₆ Nanoclusters (M = Pt, Pd)

Abstract

This paper describes the effects of doped metals on hydrogen evolution reaction (HER) electrocatalyzed by atomically controlled MAu 24 and M 2 Au 36 nanoclusters, where M = Pt and Pd. HER performances, such as onset potential (E onset ), catalytic current density, and turnover frequency (TOF), are comparatively examined with respect to the doped metals. Doping Pt or Pd into gold nanoclusters not only changes the electrochemical redox potentials of nanoclusters but also considerably improves the HER activities. E onset is found to be controlled by the nanocluster's reduction potential matching the reduction potential of H + . The higher catalytic current and TOF are observed with the doped nanoclusters in the order of PtAu 24 > PdAu 24 > Au 25 . The same trend is observed with the Au 38 group (Pt 2 Au 36 > Pd 2 Au 36 > Au 38 ). Density functional theory calculations have revealed that the hydrogen adsorption free energy (ΔG H ) is significantly lowered by metal-doping in the order of Au 25 > PdAu 24 > PtAu 24 and Au 38 > Pd 2 Au 36 > Pt 2 Au 36 , indicating that hydrogen adsorption on the active site of nanocluster is thermodynamically favored by Pd-doping and further by Pt-doping. The doped metals, albeit buried in the core of the nanoclusters, have profound impact on their HER activities by altering their reduction potentials and hydrogen adsorption free energies.

Gold nanoclusters as electrocatalysts: size, ligands, heteroatom doping, and charge dependences

“…[Au 25 (PET) 18 ] 0 , [Au 38 (PET) 24 ] 0 , [Au 130 (PET) 50 ] 0 , [Au 144 (PET) 60 ] 0 , and [Au 329 (PET) 84 ] 0 ( Fig. S1 †) were used to elucidate the dependence of catalytic activity on the number of constituent atoms.…”

“…S1 †) were used to elucidate the dependence of catalytic activity on the number of constituent atoms. To evaluate the dependence of catalytic activity on ligand functional groups, [Au 25 (PET) 18 ] 0 , hexanethiolate (C6T)-protected [Au 25 (C6T) 18 ] 0 , and dodecanethiolate (C12T)-protected [Au 25 (C12T) 18 ] 0 were used ( Fig. S1(a) and S2 †).…”

“…S1(a) and S2 †). In addition, [Au 25 (PET) 18 ] 0 , [Au 20.5 Ag 4.5 (PET) 18 ] 0 , [Au 23.7 Cu 1.3 (PET) 18 ] 0 , and [Au 24 Pd(PET) 18 ] 0 were used to investigate how the heteroatom species affect the catalytic activity ( Fig. S3 †).…”

“…[Au 25 (PET) 18 ] 0 and [Au 25 (PET) 18 ] − were used to evaluate the dependence of catalytic activity on the charge state of the cluster. Matrixassisted laser desorption/ionization (MALDI) mass spectrometry and optical absorption spectroscopy confirmed that all eleven types of clusters (Table 1) were synthesized with high purity ( Fig.…”

Controllable Conversion of CO2on Non‐Metallic Gold Clusters

“…[8] With the evolution of electronic structures from metallic to non-metallic state,these clusters can reveal ahidden mystery in the catalytic field:t he non-metallic cluster-catalysts may have similar or even superior catalytic abilities compared to the metallic ones.More than that, they are opening up anew era for catalytic science.F or example,t hese clusters provide exciting opportunities to map out the explicit structure-property relationship and allow for identification of active sites with atomic precision. [9][10][11][12][13][14][15] Specifically,they can be used to explore how the catalytic performance can be tailored by only one atom alteration. [16,17] They can also circumvent the sluggish kinetics of electron transfer for non-photosynthetic bacteria to enable photosynthesis of acetic acid from CO 2 .…”