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Progress in Chemistry 2022, Vol. 34 Issue (9): 1896-1910 DOI: 10.7536/PC211028 Previous Articles   Next Articles

• Review •

Preparation and Application of Palladium-Copper Nano Electrocatalysts

Chunyi Ye, Yang Yang, Xuexian Wu, Ping Ding, Jingli Luo, Xianzhu Fu()   

  1. College of Material Science and Engineering, Shenzhen University, Shenzhen 518055, China
  • Received: Revised: Online: Published:
  • Contact: *e-mail: xz.fu@szu.edu.cn
  • Supported by:
    Shenzhen Science and Technology Program(JCYJ20200109110416441)
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Nanomaterials that contain noble metal palladium are kinds of electrocatalytic materials which have excellent properties. Among them, Pd-Cu binary materials have attracted much attention in recent years due to their low cost and high activity. The introduction of Cu not only reduces the amount of Pd, but also causes ligand effect, stress effect, aggregation effect and so on, which provides a variety of ways to optimize the electrocatalytic performance. Constructing special morphology and structure can make the catalyst expose more active sites to increase the electrochemical active surface area and improve the electrocatalytic performance. In addition, the adjustment of Pd-Cu component or the construction of composite structure can adjust the d-band center, thereby optimizing the electrode interface adsorption energy, and finally enhancing activity and improving stability. This review summarizes some preparation methods of Cu-Pd nano electrocatalysts with different structures, such as spherical particles, porous structure, branched structure, hollow nanocage, core-shell structure and single atom. In addition, the application of Cu-Pd nano electrocatalysts in organic small molecule oxidation (such as methanol, ethanol, formic acid oxidation), inorganic small molecule reduction (such as oxygen reduction, carbon dioxide reduction) and electroless copper plating is also summarized. Finally, the development prospect of Cu-Pd nano electrocatalyst is presented.

Contents

1 Introduction

2 Structure and preparation of Pd-Cu nano electrocatalyst

2.1 Porous structure

2.2 Branched structure

2.3 Hollow structure nanocages

2.4 Core-shell structure

2.5 Spherical nanoparticles

2.6 Pd-Cu single atom dispersion electrocatalysts

3 Application of Pd-Cu nano electrocatalysts in oxidation of small organic molecules

3.1 Methanol oxidation reaction (MOR)

3.2 Ethanol oxidation reaction (EOR)

3.3 Formic acid oxidation reaction (FAOR)

3.4 Glucose oxidation reaction

4 Application of Pd-Cu nano electrocatalyst in reduction of inorganic small molecule

4.1 Oxygen reduction reaction (ORR)

4.2 CO2 reduction reaction

4.3 Reduction of N2 to ammonia, reduction of N2O and hydrogen evolution reaction (HER)

5 Application of Pd-Cu nano electrocatalyst in electroless copper plating

6 Conclusion and prospect

Key words: Pd-Cu binary material, core-shell structure, single atom, nanoparticle, electrocatalysts
Fig.1 SEM image (a) and XRD patterns (b) of PdCu alloy with porous structure[19]
Fig.2 (a) Structure diagram of PdCu/VrGO. (b) XRD patterns of NPC and nanotubular mesoporous PdCu bimetallic electrocatalysts; (c) TEM image of nanotubular mesoporous PdCu bimetallic electrocatalysts[29]
Fig. 3 XRD (a) and TEM (b) images of PdCu alloy nanodendrites[31]
Fig. 4 Schematic illustration of the formation process for bowl-like, apple-like, and spherical PdCu alloy hollow microparticles[13]
Fig. 5 SEM images of apple-like (a), bowl-like (b) PdCu alloy hollow microparticles[13]. SEM (c) and TEM (d) images of porous octahedral PdCu nanocages[32]. SEM (e) and TEM (f) images of PdCu alloy flower-like Nanocages[33]
Fig. 6 TEM images and particle size distribution histogram ofCGCu1Pd1 NS/C-HT (a) andCGCu1Pd1@PtML NS/C-HT (b); (c) Schematic illustration of the formation process forCGCu1Pd1@PtML NS/C-HT[1]
Fig. 7 (a) Schematic illustration of the formation process for PdCu/rGO; (b) TEM image of PdCu/rGO[44]
Fig. 8 (a) HAADF-STEM image of Cu5Pd/Al2O3; (b) Size distribution of the nanoparticles; (c) Elemental map of the Pd + Cu overlayer, as acquired by EDS; (d) High-resolution image of a single nanoparticle[48]
Fig. 9 (a) Schematic illustration of direct methanol fuel cell[9]; CV curves (b) and histogram of specific and mass activities (c) of IL/PdCu and Pd/C with different atomic ratios in 1 mol/L KOH containing 1 mol/L methanol[9]
Fig. 10 (A) TEM image of oxide-rich Pd0.9Cu0.1/C. (B) Linear sweep voltammetry (LSV) curves of: (a) Pd/C; (b) oxide-rich Pd0.6Cu0.4/C; (c) oxide-rich Pd0.7Cu0.3/C; (d) oxide-rich Pd0.8Cu0.2/C; (e) oxide-rich Pd0.9Cu0.1/C; and (f) oxide-rich Pd0.95Cu0.05/C in deaerated 1 M NaOH containing 1 M C2H5OH. Scan rate: 10 mV/s[50]
Fig. 11 CV curves (a) and i-t curves (b) of PdCu with different ratios in formic acid[19]
Fig. 12 TEM image and CV curves in formic acid of monodisperse PdCu alloy nanocatalysts with different ratios[28]
Fig. 13 (a) SEM image of the urchin-like Pd@CuO-Pd yolk-shell nanocompositions; (b) CV curves of the modified electrodes in N2-saturated 0.1 mol/L KOH solution in the presence of 3 mmol/L glucose at a scan rate of 100 mV/s[59]
Fig. 14 TEM (a) and HRTEM (b) images of Pd-Cu4/C. RDE curves (c) and CV curves (d) of Pd-Cu/C electrocatalyst before (the dashed lines) and after (the solid lines) ADTs for 1000 cycles[41]
Fig. 15 (a) Schematic illustration of Pd/Cu alloy; (b) d-Band center shifts for Pd and Cu surface atoms in alloy particles with respect to the pure Pd and Cu particles[62]
Fig. 16 Representative ORR electrocatalytic activity (shown in both Tafel plot and bar chart) of the five electrocatalysts in O2-saturated 0.1 mol/L (a and b) KOH and (c and d) HClO4 solutions[1]
Fig. 17 (a) TEM image of Cu-Pd-0.3; (b) the CO and H2 Faradaic efficiency at a fixed potential of -0.87 V[14]
Fig. 18 (a) Atomic-resolution HAADF-STEM image; (b) Magnified atomic-resolution HAADF-STEM image of the yellow-frame area in (a). NH3 yield rates (c) and Faradaic efficiencies (d) of PdCu/NC, Pd/NC and Cu/NC[46]
Fig. 19 SEM images of electroless copper plating on FR-4 epoxy substrate that treated by 25 mmol/L Cu@Pd colloid[15]
Fig.20 (a)Images of screen printing and electroless copper plating on A4 paper, and resistance change during bending test[44]; (b) The University of Amsterdam logo plated on a silicon rubber plate[76]
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