Efficient stabilization of in situ fabrication of PtxPd1-x nanostructures for electro-oxidation of methanol in alkaline medium

Different binary Pt_xPd_1-x alloys supported on Vulcan carbon XC-72R were synthesized by the displacement of ligands from organometallic compounds to be used as anodic electrode for methanol electro-oxidation in alkaline medium. The influence of the Pd addition during the synthesis of Pt_xPd_1-x alloys in presence of octylamine as stabilizer was analyzed in terms of structure, chemical composition and electroactivity in the methanol oxidation reaction. The X-ray photoelectron spectroscopy analysis showed that the surface of the electrodes consisted of a metallic mixture and oxide states, which confirmed the change in the electronic properties during the alloy formation. The current density of Pt₃₀Pd₇₀/C during CV measurements was about 2.1 times higher than the one observed with Pt/C electrodes. The CO tolerance was also slightly improved under similar conditions. The work findings indicate that stabilized Pt₃₀Pd₇₀/C binary alloys can be used to design highly active anodic catalysts with potential applications in direct methanol fuel cells (DMFCs).     

Displacement triangular Ag/Pd nanoplate as methanol- tolerant electrocatalyst in oxygen reduction reaction

Porous triangular Ag/Pd nanoplates with different alloy ratios, including Ag₁₈Pd₁, Ag₁₈Pd_1.5, and Ag₁₈Pd₂, were successfully prepared by a galvanic displacement reaction. These alloy nanoplates were then used as methanol-tolerant electrocatalysts in an alkaline oxygen reduction reaction (ORR). Electrochemical measurements were conducted using an ultrathin film rotating ring-disk electrode. The mass activity was found to decrease in the order Ag₁₈Pd₁ > Ag₁₈Pd₂ > Ag₁₈Pd_1.5 > Pt nanoparticles > Pd nanoparticles, similar to an observation made in a past analysis of the nanoplates in an electrolyte of free methanol; this indicates that these nanoplate catalysts are more economical than Pd nanoparticles, and even Pt nanoparticles. Additionally, compared to the reactive direction in the case of Pt and Pd nanoparticles toward methanol oxidation in an ORR electrolyte with methanol, all Ag/Pd nanoplate catalysts experienced cathodic currents, which indicate that ORRs occurred even in the presence of methanol. Despite working in a methanol-tolerant solution, the prepared alloy nanoplates still exhibited high electroactivity.     

One-step electroless deposition of Pd/Pt bimetallic microstructures by galvanic replacement on copper substrate and investigation of its performance for the hydrogen evolution reaction

A facile and one-step method for fabrication of Pd/Pt bimetallic microstructure using galvanic replacement reaction is presented. This electroless deposition was performed without any additive reagent via simple immersion of the copper sheet in cation aqueous solution of Pd and Pt. The as-prepared electrode was characterized by using the techniques of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and cyclic voltammetry and tested for the hydrogen evolution reaction (HER) in the acidic media. Comparison of the HER on the Pd/Pt bimetallic catalysts with different Pd:Pt percentage compositions indicated that the Pd₆₀Pt₄₀ catalyst had the highest HER activity among all the Pd/Pt catalysts and a better performance than the pure Pt. The effects of galvanic replacement time and concentration of H₂SO₄ on the catalytic activity of as-prepared electrode for HER were comparatively investigated.     

Effects of Pd substitution on the electrochemical properties of Mg0.9−xTi0.1PdxNi (x = 0.04–0.1) hydrogen storage alloys

Amorphous Mg_0.9−xTi_0.1Pd_xNi (x = 0.04–0.1) hydrogen storage alloys were prepared by mechanical alloying (MA). The effects of Pd substitution on the electrochemical properties of the Mg_0.9−xTi_0.1Pd_xNi (x = 0.04–0.1) electrode alloys were studied by cyclic charge–discharge, linear polarization, anodic polarization, electrochemical impedance spectroscopy (EIS), and hydrogen diffusion coefficient experiments. It was found that the cyclic capacity retention rate C₅₀/C₁ of the quaternary alloys was greatly improved due to the substitution of Pd for Mg. Mg_0.8Ti_0.1Pd_0.1Ni electrode alloy retained the discharge capacity above 200 mAh g⁻¹ even after 80 charge–discharge cycles, possessing the longest cycle life in the studied quaternary alloys. The improvement of cycle life was ascribed to the formation of passive film on the surface of these electrode alloys. X-ray photoelectron spectroscopy (XPS) analysis proved that the passive film was composed of Mg(OH)₂, TiO₂, NiO, and PdO, which synergistically protected the alloy from further oxidation. The Auger Electron Spectroscopy (AES) study revealed that the thickness of passive film increased with augmentation of the Pd content. The electrochemical impedance study of electrode alloys after different cycles demonstrated that the passive film became thicker during cycles and its thickness also increased with Pd content augmentation. It was also found that the augmentation of Pd content resulted in the decrease of exchange current density I₀ and the increase of the charge-transfer resistance R_ct. With increasing the Pd amount in the Mg_0.9−xTi_0.1Pd_xNi (x = 0.04–0.1) electrode alloys, hydrogen diffusion coefficient D was gradually enhanced at first. Then, it decreased with augmentation of cycle due to the growth of passive film on the surface of the alloys.     

Fabrication of bimetallic Cu/Pt nanoparticles modified glassy carbon electrode and its catalytic activity toward hydrogen evolution reaction

The film of poly(8-hydroxyquinoline) was formed by cyclic voltammetery method on the surface of glassy carbon electrode and poly(8-hydroxyquinoline) modified glassy carbon electrode, p(8-HQ)MGCE, was prepared. Cu²⁺ ion was adsorbed on the polymer matrix due to complexation with 8-hydroxyquinoline units Copper nanoparticles were deposited onto p(8-HQ)MGCE by applying potential and prepared copper nanoparticles galvanic replaced with platinum to fabricate poly(8-hydroxyquinoline)–Pt/Cu composite on the surface of GCE. Stripping voltammetery of Cu in aqueous 0.1 M KSCN + Britton–Robinson buffer, pH = 2.0, solution was used to quantify the copper present on the electrode surface. The amount of platinum was estimated from the electrooxidation peak of Pt in aqueous 0.1 M H₂SO₄ solution. The nature of Cu/Pt–p(8-HQ) on the surface of GCE was characterized by scanning electron microscopy. Cu/Pt–p(8-HQ) modified GCE can be used as a convenient conducting substrate for electrocatalytic hydrogen evolution reaction (HER). The effects of different parameters such as number of cycles, replacement time, scan rate of potential, and etc were investigated to obtaining optimum condition for HER.     

Pt3Y electrocatalyst for oxygen reduction reaction in proton exchange membrane fuel cells

We report here that significant electrocatalysis occurs during oxygen reduction reaction (ORR) at the Pt₃Y alloy thin film electrodes. In addition, we synthesized Pt₃Y alloy nanocatalysts for use in proton exchange membrane fuel cells, fabricated by using a high pressure sputtering technique in a gaseous mixture of Ar and He. Rather than the dense film deposited by conventional sputtering techniques, the resulting structure was comprised of a Pt₃ Y alloy nanocatalyst layer with an average particle size of 10–12 nm. The Pt₃Y alloy nanocatalysts were characterized by scanning electron microscopy, transmission electron microscopy, high-resolution X-ray photoelectron spectroscopy, and X-ray absorption near edge spectroscopy. The cell performance of the membrane electrode assembly with multiple layers of sputter-deposited Pt₃Y alloy nanoparticles and spray-deposited Nafion–carbon-ink improved dramatically compared to that obtained with the Pt only nanoparticles. The high performance of Pt₃Y alloy nanocatalysts fabricated at a sputtering pressure of 200 mTorr (Ar/He = 1) was due to miniaturization of the Pt₃Y alloy particles, formation of the porous catalyst layer, and enhancement of the kinetic activity for ORR.     

Influence of Pd addition on the electrochemical performance of Mg–Ni–Ti–Al-based metal hydride for Ni–MH batteries

Amorphous Mg_0.9Ti_0.1NiAl_0.05 and Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 alloys were prepared by high energy ball milling and evaluated as metal hydride electrodes for Ni–MH batteries. The Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 alloy showed a much higher cycle life with a capacity retention of 72% after 100 cycles (C_100th = 288 mAh g⁻¹) compared to 26% for the Pd-free alloy (C_100th = 117 mAh g⁻¹). This was mainly attributed to the improvement of the alloy oxidation resistance in KOH electrolyte with Pd addition, as confirmed by cyclic voltammetry experiments and X-ray diffraction analyses on cycled electrodes. In addition, in situ acoustic emission (AE) measurements revealed that the energy of the AE signals related to the particle cracking is lower for the Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 electrode, suggesting that the cracks are smaller in size than with the Pd-free alloy. The Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 electrode also displayed a higher discharge rate capability than the Mg_0.9Ti_0.1NiAl_0.05 electrode. On the basis of their respective electrochemical pressure–composition isotherm, it was shown that the presence of Pd in the alloy decreases the thermodynamic stability of the metal hydride. Through a comparative analysis of discharge polarization curves, it was also shown that Pd addition decreases substantially the H-diffusion resistance in the alloy whereas its positive effect on the charge-transfer resistance is limited.     

Performance and stability characteristics of MEAs with carbon-supported Pt and Pt1Ni1 nanoparticles as cathode catalysts in PEM fuel cell

Polarization curves of membrane electrode assemblies (MEAs) containing carbon-supported platinum (Pt/C) and platinum-nickel alloy (Pt₁Ni₁/C) as cathode catalysts were obtained for durability test as a function of time over 1100 h at constant current. Charge transfer resistance was measured using electrochemical impedance spectroscopy and postmortem analysis such as X-ray diffraction and high-resolution transmission electron microscopy was conducted in order to elucidate the degradation factors of each MEA. Our results demonstrate that the reduced performance of MEAs containing Pt₁Ni₁/C as a cathode catalyst was due to decreased oxygen reduction reaction caused by the corrosion of Ni, whereas that of MEAs containing Pt/C was because of reduced electrochemical surface area induced by increased Pt particle size.     

Pd5Cu4Pt oxygen reduction nanocatalyst for PEM fuel cells

Carbon dispersed Pd₅Cu₄Pt nanocatalyst synthesized by chemical reduction with NaBH₄ for the oxygen reduction reaction (ORR) in acid media is investigated. Nanocatalyst is physically characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (DRX). Results demonstrate the formation of conglomerate nanometric particles ranging from 2 to 10 nm in size. Electrochemical activity is demonstrated by cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results show that the onset potential for the ORR on Pd₅Cu₄Pt is shifted by ca. 50 mV to more positive values and enhanced catalytic current densities are observed in comparison to carbon dispersed PdCu and Pd catalysts. The Pd₅Cu₄Pt tested as cathode electrode in a membrane-electrode assembly (MEA) shows a power density of 330 mW cm⁻² at 0.5 V and 80 °C, resulting an attractive low Pt content cathode nanocatalyst for PEM fuel cells.     

Titanium dioxide as support material for Pt1Pd3 toward methanol oxidation

The electrocatalytic oxidation of methanol on the Pt₁Pd₃ nanoparticles supported on rutile TiO₂ in alkaline solution is investigated. The Pt₁Pd₃ nanoparticles are prepared by the chemical co-reduction of the precursors of Pt and Pd and then loaded on TiO₂. The Pt₁Pd₃ nanoparticles with sizes of about 2–4 nm and a certain degree of aggregation are dispersed on TiO₂. The position and shape of the methanol oxidation peak on Pt₁Pd₃/TiO₂ are more similar to those on Pt/TiO₂ than those on Pd/TiO₂, while Pt₁Pd₃/TiO₂ exhibits higher catalytic activity, e.g., a significantly higher peak intensity, than Pt₁Pd₃/C, Pt/TiO₂ and Pd/TiO₂. This indicates the advantage of TiO₂ as a support material and the strong synergy between the Pt₁Pd₃ and TiO₂ and between the Pt and Pd. Moreover, Pt₁Pd₃/TiO₂ has a high tolerance for the poisoning caused by CO. Rutile TiO₂ is shown to be suitable as a support material for the Pt₁Pd₃ to achieve enhanced catalytic activity and stability.     

Electrochemical behaviour of carbon supported Pt electrocatalysts for H2O2 reduction

Carbon supported bimetallic Pt-alloys (Pt_0.75M_0.25/C, with M = Ni or Co) are investigated as novel electrode materials for H₂O₂ reduction in acid solution. The alloy electrocatalysts, Pt_0.75Ni_0.25/C and Pt_0.75Co_0.25/C, as well as carbon supported Pt (Pt/C) are characterised using cyclic voltammetry. The electrocatalytic activity of the materials is studied using a rotating disc electrode system with a combination of linear scan voltammetry and chronoamperometry. It is found that the activity of Pt_0.75M_0.25/C electrocatalysts for H₂O₂ reduction is comparable to the activity of Pt/C electrocatalyst, with Pt_0.75Co_0.25/C exhibiting the best performance.     

Effect of MWCNTs and lithium modified MWCNTs on electrochemical hydrogen storage properties of Co0.9Cu0.1Si alloy

Mechanical alloying technique was used to prepare the Co_0.9Cu_0.1Si alloy. Composite materials of Co_0.9Cu_0.1Si doping with different amounts of multi-walled carbon nanotubes (MWCNTs) or lithium modified MWCNTs (Li-MWCNTs) were obtained via ball-milling to improve the hydrogen storage performance of Co_0.9Cu_0.1Si. XRD, SEM and TEM were used to analysis the structural properties of the samples. A three-electrode battery system was carried out to test the electrochemical properties. After the addition of MWCNTs, the composites showed higher discharge capacity, stronger HRD, better cyclic stability and lower charge-transfer resistance than the original Co_0.9Cu_0.1Si alloy. The electro-catalytic function of MWCNTs, the reduction of particle size and the raise of specific surface area for Co_0.9Cu_0.1Si alloy may provide larger electrochemically accessible area and rapid channel for hydrogen transportation, which are important to enhance the electrochemical performance of the alloy. Moreover, a further improvement was achieved after the addition of Li-MWCNTs, illustrating that the MWCNTs and lithium species had synergistic effects in improving the discharge capacity and reaction kinetics of the Co_0.9Cu_0.1Si alloy electrode. As the weight ratio of the alloy and Li-MWCNTs was 15:1, the optimal discharge capacity of 624.4 mAh/g and the highest capacity retention of 67.5% were achieved.     

Performance of membrane electrode assemblies using PdPt alloy as anode catalysts in polymer electrolyte membrane fuel cell

Pd-based nanoparticles, such as 40 wt.% carbon-supported Pd₅₀Pt₅₀, Pd₇₅Pt₂₅, Pd₉₀Pt₁₀ and Pd₉₅Pt₅, for anode electrocatalyst on polymer electrolyte membrane fuel cells (PEMFCs) were synthesized by the borohydride reduction method. PdPt metal particles with a narrow size distribution were dispersed uniformly on a carbon support. The membrane electrode assembly (MEA) with Pd₉₅Pt₅/C as the anode catalyst exhibited comparable single-cell performance to that of commercial Pt/C at 0.7 V. Although the Pt loading of the anode with Pd₉₅Pt₅/C was as low as 0.02 mg cm⁻², the specific power (power to mass of Pt in the MEA) of Pd₉₅Pt₅/C was higher than that of Pt/C at 0.7 V. Furthermore, the single-cell performance with Pd₅₀Pt₅₀/C and Pd₇₅Pt₂₅/C as the anode catalyst at 0.4 V was approximately 95% that of the MEA with the Pt/C catalyst. This indicated that a Pd-based catalyst that has an extremely small amount of Pt (only 5 or 50 at.%) can be replaced as an anode electrocatalyst in PEMFC.     

Pd9Au1@Pt/C core-shell catalyst prepared via Pd9Au1-catalyzed coating for enhanced oxygen reduction

The scarcity and poor long-term stability of Pt has greatly hindered its commercial application as oxygen reduction reaction (ORR) catalyst. In this work, carbon-supported Pd₉Au₁ alloy particles with a Pd/Au molar ratio of 9:1 synthesized by using an ethylene glycol-based reduction method were used to catalyze ethanol oxidation to coat Pd₉Au₁ core with Pt atomic layers to synthesize Pd₉Au₁@Pt/C catalyst. Physical characterization shows that the as-synthesized Pd₉Au₁@Pt/C catalysts present a well-defined core-shell structure and the surface Pt layers can be well controlled by tuning the amount of Pt precursor added during synthesis. Electrochemical characterization shows that among the synthesized catalysts Pd₉Au₁@Pt₂/C with 2 atomic Pt layers exhibits the best activity and excellent stability for ORR, as evidenced by its even increased half-wave potential after 10000 potential cycles between 0.6 and 1 V in O₂-saturated 0.1 M HClO₄ solution. This enhanced ORR activity and stability of Pd₉Au₁@Pt₂/C catalyst can be attributed to the compressive strain and stabilizing effect of Pd₉Au₁ core on Pt shell.     

Study on the role of Pt and Pd in Pt–Pd/TiO2 bimetallic catalyst for H2 oxidation at room temperature

The hydrogen safety issue is spotlighted as the hydrogen process is extended. For this reason, we studied catalysts for H₂ oxidation at room temperature to ensure hydrogen safety. Catalysts were prepared by different preparation methods and compared to evaluate the role of Pt and Pd in Pt–Pd/TiO₂ catalysts. The catalytic activity was significantly enhanced when activity metal size was small and it was exposed to catalyst surface to a high Pd ratio. For the 0.1%Pt-0.9%Pd/TiO₂ catalyst, high hydrogen conversion of 90% was obtained under the condition of 0.5% hydrogen injection. To understand the correlation between activity and characteristics of catalyst, the physicochemical characteristics of the various catalysts were investigated by X-ray photoelectron spectroscopy (XPS), temperature-programmed oxidation and reduction (TPOR) and Field Emission-Transmission Electron Microscope (FE-TEM) analysis. From these analysis, it was found that Pt served the role of highly dispersion of active metal (Pt–Pd) and as with increasing Pd ratio of active metal, hydrogen activity was increased, which indicates that hydrogen oxidation had proceeded on the Pd site. Finally, the valence state of the Pd influenced hydrogen oxidation activity of Pt–Pd/TiO₂, which increased with increasing ratio of Pd⁰/Pd_Total.     

Glassy carbon electrode modified by Pd–Cu bimetallic nano-dendrites film decorated on the reduced graphene oxide using galvanic replacement as a low-cost anode in methanol fuel cells

Glassy carbon electrode (GCE) modified by reduced graphene oxide Cu–Pd nano-dendrimer (Pd-CuNDs-RGO/GCE) was prepared using electro-deposition and spontaneous displacement methods. Graphene oxide was put on the surface of GCE by drop-casting, then a thin film of reduced graphene oxide (RGO) was formed by electro-reduction at ?0.9 V. The copper nano-dendrimers (CuNDs) were electro-plated on RGO/GCE surface. Finally, Pd-CuNDs-RGO/GCE was prepared by the spontaneous replacement of CuNDs with palladium nanoparticles (PdNPs) in a dilute solution of palladium. The electrode surface was characterized using field-emission scanning electron microscopy (FESEM), X-ray energy diffraction (EDX) spectroscopy, and electrochemical techniques. The electrochemical behavior of the modified electrode in the oxidation of alkaline solution of methanol was investigated. The experimental conditions affecting the performance of the modified electrode in the methanol oxidation were studied and optimized. Finally, the proposed electrode has the onset potential of ?0.5 V and the ratio of i_f/i_b equal to 2.2, which confirms the high catalytic activity. The electrode has appropriate stability and shows about 86% of initial activity after 100 times testing.     

One-pot sonication-assisted polyol synthesis of trimetallic core–shell (Pd,Co)@Pt nanoparticles for enhanced electrocatalysis

In this report, the synthesis and characterization of trimetallic (Pd,Co)@Pt nanoparticles (NPs) with Pt-enriched surfaces are detailed. (Pd,Co)@Pt NPs supported on carbon with different elemental compositions (Pd₅₀Co₂₀Pt₃₀, Pd₃₄Co₂₇Pt_39, and Pd₂₁Co₃₄Pt₄₅) are synthesized by sonochemical reactions of Pt(acac)₂, Pd(acac)₂, and Co(acac)₂ in ethylene glycol. The NPs are subsequently characterized by X-ray diffractometry, transmission electron microscopy, and inductively coupled plasma − atomic emission spectroscopy to determine their particle size, morphology, and elemental composition. The existence of a Pt-enriched surface on the (Pd,Co)@Pt NPs is demonstrated by line profiles obtained via scanning transmission microscopy − energy dispersive spectroscopy. The NPs are applied to electrocatalysis for oxygen reduction reactions. When compared to a commercial Pt catalyst, the onset potential of the NPs increased by 22 mV, while the specific and mass activities were enhanced by factors of ∼ 2.7–4.9 and 4.3–6.3, respectively. The (Pd,Co)@Pt NPs also showed superior stability, as the onset potential was reduced by 11–19 mV after 5000 potential cycles when compared to the 45 mV reduction observed for a commercial Pt catalyst.     

Effects of surface coating with Cu-Pd on electrochemical properties of A2B7- type hydrogen storage alloy

La_0.75Mg_0.25Ni_3.2Co_0.2Al_0.1 hydrogen storage alloy, the nickel-metal hydride (MH/Ni) secondary battery negative electrode, was modified by CuSO₄ solution (3 wt% in Cu in contrast with alloy weight) and PdCl₂ solution varied from 1 wt% to 4 wt% in Pd in contrast with alloy weight with a simplified pollution-free replacement plating method, aiming at improving its comprehensive electrochemical properties. The XRD analysis and SEM images combined with EDS results reveal that Cu and Pd nanoparticles are uniformly plated on the pristine alloy surface. The relative amount of Pd on the Cu-Pd coated alloy surface increases notably as the PdCl₂ concentration increases in the plating solution. Electrochemical tests indicate that alloy electrodes modified by Cu-Pd composite coating show perfect activation performance, which achieve the maximum discharge capacity at the first charge-discharge cycle. Moreover, alloy electrodes coated with Cu-Pd perform dramatically enhanced high rate dischargeability (HRD). The enhancement increases firstly and then decreases as the content of Pd increases in the Cu-Pd coating. Meanwhile, the cycle life of modified alloys is also improved significantly. Among all the samples, the Cu-Pd coated alloy with 3 wt% Pd content in the PdCl₂ solution reinforces the comprehensive electrochemical properties most sufficiently, with dischargeability of 86.4% under 1500 mA/g and remaining capacity of 82.7% after 100 cycles.     

Nanoporous (Pt1-xCox)3Al intermetallic compound as a high-performance catalyst for oxygen reduction reaction

Nanocatalysts that boost the sluggish kinetics of oxygen reduction reaction with a long-term durability are crucial for widespread use of low-temperature fuel cells. Here we report a nanoporous intermetallic compound typically composed of platinum–cobalt–aluminum intermetallic core with in-situ grown atomic-layer-thick Pt skin as a novel oxygen-reduction-reaction nanocatalyst with remarkably enhanced performance. Both Pt and Co atoms thermodynamically prefer to locate nearby Al element within face-centered cubic Pt₃Al matrix via the formation of strong PtAl and CoAl bonds, which not only enable synergistic ligand and compressive strain effects to moderately weaken the oxygen adsorption energy of Pt skin, but alleviate the evolution of surface Pt atoms to protect against the further dissolution of less-noble Co and Al. As a result, the nanoporous platinum–cobalt–aluminum nanocatalyst exhibits specific activity of 3.40 mA cm^?2_Pt and mass activity of 2.2 A mg^?1_Pt for the oxygen reduction reaction at 0.9 V versus reversible hydrogen electrode (～13- and ～20-fold enhancement relative to commercially available platinum nanoparticles supported carbon) with an exceptional durability, showing genuine potential as cathode catalyst in next-generation electrochemical energy conversion devices.     

Methanol and ethanol oxidation on carbon supported nanostructured Cu core Pt–Pd shell electrocatalysts synthesized via redox displacement

Six different carbon-supported Cu core Pt–Pd shell (Cu@Pt–Pd) catalysts have been successfully synthesized by the galvanic replacement of Cu atoms by Pt⁴⁺ and Pd²⁺ ions at room temperature and their electrocatalytic activity for methanol and ethanol oxidation have been evaluated in acid media. Cu@Pt–Pd core shell nanoparticles with a narrow size distribution and an average diameter in the range of 3.1–3.5 nm were generated onto the carbon support. The compositional and the structural analysis of the as-prepared materials pointed out that the nanoparticles are formed by a Cu rich core covered by a Pt–Pd rich shell due to the interdiffusion of the metals after the galvanic replacement reaction. The electrocatalytic properties of the Cu@Pt–Pd electrodes in the electro-oxidation of methanol and ethanol was found to be dependent on the electrochemical surface area, lattice strain of the surface, composition and thickness of the Pt–Pd shell surrounding the Cu core. The optimum catalyst composition to obtain the best performance for methanol and ethanol electro-oxidation was determined to be Pt_0.59Pd_0.324Cu_0.167/C (6.2 wt.% Pt, 2.2 wt.% Pd and 0.7 wt.% Cu). This catalyst has a greatly enhanced mass activity, lower onset potential and poisoning rate, and higher turnover number in the MOR and EOR reactions compared to a commercial Pt_0.51Ru_0.49/C (20 wt.% Pt and 10 wt.% Ru). Consequently, this simple preparation method is a viable approach to making a highly active catalyst with low platinum content for application in direct alcohol fuel cells (DAFCs).