Ultrasmall Pd‐Cu‐Pt Trimetallic Twin Icosahedrons Boost the Electrocatalytic Performance of Glycerol Oxidation at the Operating Temperature of Fuel Cells

Abstract

Recently, in order to improve the energy conversion efficiency of direct polyol fuel cells, the engineering of effective Pd‐ and/or Pt‐based electrocatalysts to rupture CC bonds has received increasing attention. Here, an example is shown to synthesize highly uniform sub‐10 nm Pd‐Cu‐Pt twin icosahedrons by controlling the nucleation phase. Because of the synergies of the electronic effect, synergistic effect, geometric effect, and abundant surface active sites originating from the formation of near surface alloy and special icosahedral shape, the Pd‐Cu‐Pt twin icosahedrons exhibit excellent electrocatalytic performance in glycerol electrocatalysis at the operating temperature of direct alcohol fuel cells (70 °C) in KOH electrolyte. The Pd50.2Cu38.4Pt11.4 icosahedrons show mass activities of 9.7 A mg−1Pd+Pt and 13.7 A mg−1Pd. Furthermore, the Pd50.2Cu38.4Pt11.4 icosahedrons demonstrate long‐term durability in current–time test for 36 000 s and high in situ anti‐CO poisoning performance. In addition, the introduction of CO can enhance electro‐oxidation endurance on Pd50.2Cu38.4Pt11.4 icosahedrons, and the peak mass activity can reach to 14.4 A mg−1Pd+Pt. The in situ Fourier transform infrared spectroscopy spectra indicate that the Pd50.2Cu38.4Pt11.4 icosahedrons possess a high capacity to break CC bonds and may efficiently convert glycerol into CO2, thus improving the utilization efficiency of energy‐containing molecule glycerol.

Progress and Perspectives in Photo‐ and Electrochemical‐Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production

“…Trimetallic electrocatalyst can combine the different mechanisms mentioned above, and offer even more flexibility toward catalyst tuning. [177,178,180,[184][185][186][187] As a result, trinary catalysts are among the ones exhibiting higher mass and specific activities with low peak potential (Figure 12). For example, Kim et al developed a PtRuSn/C trinary electrocatalyst with atomic ratio of 5:4:1.…”

Recent Progress in Electrocatalytic Glycerol Oxidation

“…[ 20 ] As research continues, the performance of GOR involved fuel cells is constantly improved. [ 21,35 ] Martins et al fabricated an Fe‐decorated Pt/C‐modified carbon paper anode and applied in an assembled fuel cell that couples alkaline GOR reaction with acidic oxygen reduction reaction (ORR). Such a fuel cell achieved a peak power density up to 53.6 mW cm −2 at 694 mV and a limit current density up to 98.0 mA cm −2 because of high activity of the prepared catalysts and the well‐designed structure of fuel cell.…”

“…Moreover, Pd 50.2 Cu 38.4 Pt 11.4 IHs possessed the best stability with the least fluctuation of current density during 1 h electrolysis (Figure 3c), as well as the best anti‐poisoning ability to CO (Figure 3d). In situ FTIR analysis indicated that the Pd 50.2 Cu 38.4 Pt 11.4 IHs can break CC bond in glycerol at low potential and directly convert generated intermediates into CO 2 , circumventing the pathway of forming adsorbed CO. [ 35 ] The enhanced GOR performance over Pd–Cu–Pt IHs can be assigned to synergies of electronic effect, synergistic effect, and geometric effect stemmed from the formed near surface alloy and special IH shape.…”

Solvent‐Mediated Shell Dimension Reconstruction of Core@Shell PdAu@Pd Nanocrystals for Robust C1 and C2 Alcohol Electrocatalysis

“…[ 16–18 ] However, most synthesis and regulation of core@shell structures focus on the single dimension engineering, such as the fabrication of 1D Au@PdPb NWs, [ 19 ] 2D Pd@PtCu nanoplates, [ 20 ] lacking the systematic yet pointed control on core@shell structures with multiple dimensions modulation, such as the shell dimension tuning. [ 21–23 ] Meanwhile, the rational dimension tuning in core@shell structures is of great significance to the catalytic performance, which could offer rich active sites and proper adsorption energy for superficial intermediates, emerging an advanced strategy for catalytic property enhancement. [ 24–26 ]…”