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.     

Carbon supported nano-sized Pt–Pd and Pt–Co electrocatalysts for proton exchange membrane fuel cells

Nano-sized Pt–Pd/C and Pt–Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt–Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H₂, CO and H₂–CO mixtures, the Pt–Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt–Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt–Pd/C and Pt–Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3–4 nm. It was found that while the Pt–Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt–Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H₂ and O₂ gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt–Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt–Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.     

PANI-modified Pt/Na4Ge9O20 with low Pt loadings: Efficient bifunctional electrocatalyst for oxygen reduction and hydrogen evolution

Exploring cost-effective electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) have been a goal in the sustainable hydrogen-based society. Although abundant of alternative materials have been developed, Pt/C remains the most efficient electrocatalyst for the ORR and HER. Nevertheless, improving the stability and reducing Pt loading for Pt-based electrocatalysts are still big challenges. Herein, semiconductor crystals Na₄Ge₉O₂₀ with richer topology structure was chosen as electrocatalyst support, subsequently, the conductive polymer polyaniline (PANI) was decorated on semiconductor Na₄Ge₉O₂₀, low-content Pt nanoparticles (Pt NPs) with the size of 1–3 nm were then uniformly anchored on the surface of Na₄Ge₉O₂₀-PANI to obtain the efficient bifunctional electrocatalyst for ORR and HER in the acidic solution. More importantly, the stability and mass activity of the obtained electrocatalyst 5 wt% Pt/Na₄Ge₉O₂₀-PNAI are significantly higher than that of commercial 20 wt% Pt/C for ORR and HER. It was proposed that the PANI could not only promote the electron transfer from Na₄Ge₉O₂₀ to Pt, but also stabilize the Pt NPs, thus, improving the electrocatalytic activity and stability of 5 wt% Pt/Na₄Ge₉O₂₀-PNAI.     

Efficient hydrogen evolution catalysis triggered by electrochemically anchored platinum nano-islands on functionalized-MWCNT

We report the electrochemical deposition (ECD) of platinum nano-islands (Pt NIs) on functionalized multi-walled carbon nanotubes (ECD Pt NIs@f-MWCNT) as an efficient electrocatalyst for the hydrogen evolution reaction (HER). Pristine MWCNT was acid treated to induce the number of oxygen functional groups on the surface and enhances the wettability. Thereafter, Pt nanoparticles (Pt Nps) were deposited by a simple electrodeposition technique on the oxygen enriched MWCNT surface. The Pt NIs@f-MWCNT has been physicochemically characterized using X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy and X-ray photoelectron Spectroscopy (XPS). The TEM analysis showed the presence of Pt NIs on MWCNT wherein, the NIs were made up of small Pt nanoclusters of ～4 nm in dimension. The electrochemical HER studies were carried out using linear sweep voltammetry (LSV), Tafel polarization and electrochemical impedance spectroscopy (EIS). An overpotential (?) of ?84 mV was obtained at a current density (j) of ?10 mA/cm². The amount of Pt loading has been optimized through electrodeposition. Enhanced HER activity was observed with a Pt loading of 3.8 μg/cm². In order to ascertain the durability of the catalyst, accelerated degradation test (ADT) was carried out for 10,000 cycles at a scan rate (?) of 100 mV/s. The turnover frequency (TOF) was estimated to be 6.3 s^?1 at ? = ?70 mV.     

Nitrogen doped graphene supported Pd as hydrogen evolution catalyst for electrochemical methanol reformation

Electrochemical methanol reformation (ECMR) method has been identified as one of the most effective method for on-site hydrogen production. However, concentrated research towards the development of efficient inexpensive hydrogen evolution reaction (HER) electrocatalyst holds the pivotal role in realizing the hydrogen economy. In this context, for the first time N-graphene supported Pd (Pd/NG) was synthesised and employed as an HER catalyst in ECMR process. N-graphene was synthesised by modified Hummer's method followed by Pd deposition through hydrothermal route. The electrocatalytic activity of Pd/NG for hydrogen evolution was evaluated by CV and LSV techniques. Tafel slope of Pd/NG and Pt/C was calculated from LSV curves and was found to be 33 and 31 mV/decade, respectively. Exchange current density was found to be 3.6 and 3.2 × 10⁻⁴ A cm⁻² for Pd and Pt catalysts, respectively. The enhanced electrocatalytic activity is majorly attributed to the N-doping and uniform distribution of Pd nano particles on graphene. Further, the performance of Pd/NG was also evaluated in single ECMR cell using Pt–Ru/C at anode and Pd/NG at cathode as electrocatalysts. The results indicated the suitability of Pd/NG as cathode electrocatalyst for HER in ECMR process.     

Platinum-antimony doped tin oxide nanoparticles supported on carbon black as anode catalysts for direct methanol fuel cells

Antimony doped tin oxide supported on carbon black (ATO/C) has been synthesized using an in situ co-precipitation method, and platinum-ATO/C nanoparticles have been prepared using a consecutive polyol process to enhance the catalyst activity for the methanol oxidation reaction. The Pt-ATO/C electrocatalyst is characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microcopy (SEM), energy dispersive X-ray spectroscopy (EDS) and cyclic voltammetry. The Pt-ATO/C catalyst exhibits a relatively high activity for the methanol oxidation reaction compared to Pt-SnO₂/C or commercial Pt/C catalyst. This activity can be attributed to the high electrical conductivities of the Sb-doped SnO₂, which induces the electronic effects with Pt catalysts. Pt-ATO/C is a promising methanol oxidation catalyst with high activity for the reaction in direct methanol fuel cells.     

Characterization of Pt supported on commercial fluorinated carbon as cathode catalysts for Polymer Electrolyte Membrane Fuel Cell

Pt nanoparticles supported on carbon monofluoride (CFx), synthesized from H₂PtCl₆ using NaHB₄ as a reducing agent has been investigated as a cathode electrocatalyst in fuel cells. Surface characterization, performed by transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD), shows a homogeneous distribution and high dispersion of metal particles. Kinetic parameters for the electrocatalyst are also obtained from the steady state measurements using a rotating disk electrode (RDE) in 0.5 M H₂SO₄ solution. Analysis by Koutecky–Levich equation indicates an overall 4 e^? oxygen reduction reaction (ORR). Evaluation of the catalyst in single cell membrane electrode assemblies (MEAs) for proton exchange membrane based Direct Methanol Fuel Cell (DMFC) and H₂ Fuel Cell at different temperatures and flows of O₂ and Air are shown and compared against commercial Pt/C as the cathode electrocatalyst. Evaluation of Pt/CFx in H₂ fed fuel cells shows a comparable performance against a commercial catalyst having a higher platinum loading. However, in direct methanol fuel cell cathodes, an improved performance is observed at low O₂ and air flows showing up to 60–70% increase in the peak power density at very low flows (60 mL min^?1).     

Pt supported on mesoporous material for methanol and ethanol oxidation in alkaline medium

Pt nanoparticles supported on a mesoporous material of zeolite Faujasite-C composite is a highly active catalyst for methanol and ethanol oxidation in alkaline media. Pt was synthesized by a simple methodology of chemical reduction using ultrasound method. Faujasite-C composite was prepared by sol-gel method using fly ash as economic precursor. Pt/Faujasite-C was characterized by X-ray diffraction (XRD), scanning (SEM) and transmission (TEM) electron microscopy to investigate its structure, morphology, composition and size. The electrochemical activity of catalyst towards methanol and ethanol oxidation reaction in alkaline media was evaluated by cyclic voltammetry and chronoamperometry techniques. The results obtained were compared with Pt/C synthesized and tested at the same conditions. According to TEM results Pt/Faujasite-C electrocatalyst exhibits a higher Pt agglomeration compared to Pt/C. Pt/Faujasite-C is more active for alcohol oxidation reactions compared to Pt/C. Pt electrocatalysts are more active for ethanol oxidation than methanol oxidation. Chronoamperometric results indicated that Pt deactivation by intermediate poisoning is more severe for ethanol than methanol. Pt/Faujasite-C can be used as anodic electrocatalyst in direct liquid fuel cells.     

Effect of preparation conditions on the performance of nano Pt‒CuO/C electrocatalysts for methanol electro-oxidation

Nano PtCuO particles were deposited on Vulcan XC-72R carbon black using the impregnation and microwave irradiation methods. The prepared catalysts were characterized by XRD, TEM and EDX analyses. TEM images indicated that the microwave method provides homogeneously distributed catalyst particles in smaller size, compared to the one prepared by the impregnation method. The electrocatalytic activity of Pt?CuO/C electrocatalysts was investigated to oxidize methanol in 0.5 M H₂SO₄ solution by applying cyclic voltammetry and chronoamperometry techniques. The oxidation current density of Pt?CuO/C electrocatalyst, prepared by the microwave method, showed two folds increment with a potential shift in the negative direction by 69 and 36 mV at the first and second oxidation peaks, respectively, relative to those at the catalyst prepared by the impregnation method. The effect of varying methanol concentration on the resulting oxidation current density of Pt?CuO/C electrocatalysts was studied. Some kinetic information about the reaction order with respect to methanol and Tafel slope values was calculated. Slower current density decay was observed in the chronoamperogram of Pt?CuO/C electrocatalyst, prepared by the microwave method, reflecting a lower degree of surface poisoning.     

MnO2 modified multi-walled carbon nanotubes supported Pd nanoparticles for methanol electro-oxidation in alkaline media

A novel method to prepare MnO₂ modified multi-walled carbon nanotubes (MnO₂/MWCNTs) supported Pd (Pd-MnO₂/MWCNTs) electrocatalyst is reported. The morphology, component and crystallinity of the catalyst were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The activity of Pd-MnO₂/MWCNTs was tested using methanol electro-oxidation in alkaline media. The results showed that the Pd-MnO₂/MWCNTs exhibited higher electrocatalytic activity and stability than Pd/MWCNTs and Pd/Vulcan (Pd/commercial Vulcan XC-72 carbon black).     

Robust three dimensional N-doped graphene supported Pd nanocomposite as efficient electrocatalyst for methanol oxidation in alkaline medium

Pd nanoparticles (PdNPs) with the diameter of ～3.2 nm were successfully confined within a robust three dimensional (3D) N-doped porous graphene (R3DNG) via a polyol-assisted reduction strategy. The as-obtained PdNPs/R3DNG composite was characterized by SEM, TEM, XRD and XPS, and was conducted as electrocatalyst for methanol oxidation in alkaline medium. The results showed that PdNPs/R3DNG featured the remarkable electrocatalytic activity (2.71 A mg^?1 Pd) and outstanding cyclic stability (66.5% forward peak current retention after 1000 cycles), which is even superior to the state-of-the-art Pt/C catalyst. The synergistic effect between the support of R3DNG and PdNPs is believed to be responsible for the outstanding electrocatalytic performance.     

Mesoporous tungsten carbide-supported platinum as carbon monoxide-tolerant electrocatalyst for methanol oxidation

This paper reports a CO-tolerant electrocatalyst, mesoporous tungsten carbide-supported platinum (Pt/m-WC), for methanol oxidation. The support m-WC was synthesized by evaporation-induced triconstituent co-assembly method in which phenol formaldehyde polymer resin was used as the carbon precursor, tungsten hexachloride as the tungsten precursor and an amphiphilic triblock copolymers (P123) as the template. Nano-sized platinum particles were loaded on the m-WC to prepare Pt/m-WC. The structure and morphology of the prepared electrocatalyst were characterized by transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) and X-ray diffraction (XRD), and its activity toward methanol oxidation and its tolerance for CO were determined by cyclic voltammetry (CV) and chronopotentiometry (CP). It is found that the m-WC carburized at 900 °C(m-WC-900) has a larger specific surface area (182 m² g⁻¹) and a appropriate crystal structure compared to the m-WC carburized at 800 °C or 1000 °C, and thus is better as the support of platinum. The prepared Pt/m-WC-900 exhibits higher activity toward methanol oxidation and better tolerance for CO than Pt/Vulcan XC-72. The onset potential of CO electro-oxidation on Pt/m-WC is 0.449 V, which is more negative than that on Pt/Vulcan XC-72 (0.628 V).     

Aluminum supported palladium nanoparticles: Preparation,characterization and application for formic acid electrooxidation

Palladium nanoparticles were fabricated on the aluminum electrode (Pd/Al) by electrodeposition method through a single step potential from an aqueous solution of 1 mM Pd(NH₃)₄Cl₂. The electrochemical and physical characteristics of the Pd/Al were investigated by cyclic voltammetry, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) method. Electrochemical measurements in acidic solution indicate that Pd/Al exhibits significantly high electrochemical active surface area (18.32 cm²) with respect to Pd–Al (2.1 cm²) (electroless deposited) and bare Pd (0.28 cm²) electrodes. SEM images and XRD results show that the Pd particles are homogeneously deposited on the surface Al substrate in nanoparticles size between 30 and 50 nm with maximum Pd (111) plane at 2θ angles about of 39°. The Pd/Al was used as electrocatalyst for the oxidation of formic acid (FA) in 0.1 M H₂SO₄ solution. The cyclic voltammetry and chronoamperometry results show that the obtained electrocatalyst, Pd/Al, exhibits high catalytic activity and stability for the electrooxidation of FA. On the other hand, the Pd/Al electrocatalyst has higher catalytic activity for FA oxidation than the comparative Pd–Al and bare Pd electrodes and shows great potential as less expensive electrocatalyst for FA oxidation in direct formic acid fuel cells.     

Electrocatalytic activity of Pt–Pd electrocatalysts for the oxygen reduction reaction in proton exchange membrane fuel cells: Effect of supports

Pt–Pd electrocatalysts supported on different types of support including domestic Hicon Black (HB), multi-walled carbon nanotubes (MWCNT) and titania (TiO₂) were prepared by a combined approach of impregnation and seeding, and compared to that prepared using the commercial Vulcan XC-72 (C). Their oxygen reduction reaction (ORR) activities in an acid electrolyte (0.5 M H₂SO₄) and in a single proton exchange membrane (PEM) fuel cell were evaluated. The type of support was found to affect the Pt–Pd electrocatalyst morphology and ORR activity. The Pt–Pd/C electrocatalyst had the smallest Pt particle size, better catalyst dispersion and a higher Pt:Pd M ratio compared to that of other types of supported Pt–Pd electrocatalysts. However, both in the acid solution and in a single PEM fuel cell, the ORR activities of the Pt–Pd/HB and Pt–Pd/CNT electrocatalysts were comparable to that of the Pt–Pd/C one. The ORR pathway of all supported Pt–Pd electrocatalysts were close to the four-electron pathway.     

Facile galvanic replacement method for porous Pd@Pt nanoparticles as an efficient HER electrocatalyst

In realm of renewable energy, development of an efficient and durable electrocatalyst for H₂ production through electrochemical hydrogen evolution reaction (HER) is indispensable. Herein, we demonstrate a simple preparation of carbon-supported nanoporous Pd with surface coated Pt (CS–PdPt) by a simple galvanic replacement reaction (GRR). The phase purity and porosity have been confirmed by XRD, HRTEM, and N₂ sorption techniques. As HER electrocatalyst, CS-PdPt showed a low overpotential of 26 mV in 0.5 M H₂SO₄ at current density of 10 mA cm⁻², which is lower than the commercial Pt/C electrode. The CS-PdPt catalyst exhibits an overpotential of 46 mV in 1 M KOH, and 50 mV in neutral buffer (1 M PBS) at 10 mA cm⁻². The CS-PdPt furnished with small Tafel values of 33, 88, and 107 mV dec⁻¹ in acidic, alkaline, and neutral medium, respectively. Accelerated durability test at 100 mV s⁻¹ for 1000 cycles demonstrated a negligible change in HER activity.     

Graphene oxide supported Pd-Fe nanohybrid as an efficient electrocatalyst for proton exchange membrane fuel cells

The experimental realization and computational validation for graphene oxide (GO) supported palladium (Pd)-iron (Fe) nanohybrids as a new generation electrocatalyst for proton-exchange membrane fuel cells (PEMFCs) has been reported. The experimental apprehension of the present catalyst system has been initiated with the graphene oxide, followed by the doping of Pd and Fe via thermal inter calation of palladium chloride and iron chloride with the in-situ downstream reduction to get nanohybrids of the GO-Pd-Fe. These nanohybrids are subsequently characterized by RAMAN, FT-IR, UV–Vis, XRD, SEM, EDS, TEM and HRTEM analysis. Furthermore, the first principle calculations based on Density Functional Theory (DFT) with semi-empirical Grimme DFT-D₂ correction has been performed to support the experimental findings. Computational results revealed the alteration of graphene electronic nature from zero-band gaped to metallic/semi-metallic on adsorption of transition metal clusters. Moreover, the defect sites of the graphene surface are more favorable than the pristine sites for transition metal adsorption owing to the strong binding energies of the former. Electrochemical studies show that GO-Pd-Fe nanohybrids catalyst (Pd: Fe = 2:1) demonstrates excellent catalytic activity as well as the higher electrochemical surface area of (58.08 m²/g Pd–Fe)⁻¹ which is higher than the commercially available Pt/C catalyst with electrochemical surface area 37.87 m²/(g Pt)⁻¹.     

Preparation of PEDOT-modified double-layered hollow carbon spheres as Pt catalyst support for methanol oxidation

In this paper, Pt nanoparticles (Pt NPs) deposited hybrid carbon support is prepared by modifying double-layered hollow carbon spheres（DLHCs）with poly(3,4-ethylenedioxythiophene) (PEDOT) and used as anode catalyst of methanol oxidation. The structure of nanocomposites is characterized by SEM, TEM, FT-IR, XRD and XPS, confirming the greatly enhanced synergistic effect between the PEDOT and DLHCs, and illustrating the uniform distribution of Pt NPs on the PEDOT/DLHCs composite surface with a small particle size (~2.63 nm). Cyclic voltammetry, chronoamperometry and impedance spectroscopy applied to determine the electrocatalytic activity of catalysts, it is found that the synthesized PEDOT/DLHCs/Pt possesses excellent characteristics such as large electrochemically active surface area and high mass activity of 59.45 m² g⁻¹ and 807 mA mg⁻¹ in 0.5 M H₂SO₄ containing 1 M methanol solution, which is almost 1.24 and 2.8 times greater than those of commercial Pt/C, and the catalyst exhibits superior stability after 500 durability cycles. The enhanced electrocatalytic behavior can be ascribed to the excellent electronic conductivity of PEDOT-modified DLHCs and the strong binding of PEDOT/DLHCs to Pt NPs, suggesting that the PEDOT/DLHCs/Pt is a promising electrocatalyst for direct methanol fuel cell.     

Fabrication of platinum thin films for ultra-high electrocatalytic hydrogen evolution reaction

While the noble metals (e.g., platinum, (Pt)) remain the benchmark electrocatalyst for the hydrogen evolution reaction (HER), their mass production require a reduced metal loading and faster fabrication protocols. The aim of the present work is to prepare Pt thin films by simple and fast fabrication technique, and to evaluate their performance for HER. The thin films of Pt are grown on two substrates, namely titanium foil (Ti) and nickel foam (NF), using a single step aerosol assisted chemical vapor deposition (AACVD) method. The film deposition time are varied from 20 to 60 min. Microscopic analyses suggest a gradual evolution of the films into percolated and/or porous nanostructures, a feature that remains highly desired to allow the maximum access of active sites. The performance of the as-prepared electrodes is evaluated by monitoring the HER in acidic electrolyte. The Pt film on nickel foam (Pt/NF) exhibits better electrical conductivity and smaller charge transfer resistance, while the film deposited on the Ti foil (Pt/Ti) demonstrates superior catalytic activity per active sites. The as-prepared Pt/Ti and Pt/NF electrodes produce 10 mA cm⁻² at overpotential of 28 mV and 26 mV, respectively, better in performance than commercial Pt/C electrode (~39 mV), set a new bench mark electrocatalyst for the HER.     

Pd/Hemin-rGO as a bifunctional electrocatalyst for enhanced ethanol oxidation reaction in alkaline media and hydrogen evolution reaction in acidic media

H₂ generation needs a cost-effective, robust, stable, long-durable, and super-active electrocatalyst. This study reveals a rapid and facile method for fabricating Pd NPs on Hemin-rGO as novel support. The obtained electrocatalyst was characterized by UV–Vis, XPS, FESEM, EDS, HRTEM, and AFM. The electrochemical measurements reveal the superb effect of Hemin-rGO for enhancing the catalytic activity of Pd as bifunctional electrocatalysts for hybrid water electrolysis (hydrogen evolution reaction (HER) and ethanol electrooxidation reaction (EOR)). Pd/Hemin-rGO displays a low peak potential (−210 V) with remarkable current density (1.95 A mg⁻¹ Pd) in 0.1 M EtOH and 0.1 M NaOH. The ratio of j_f/j_b of Pd/Hemin-rGO compared with Pd electrocatalyst reveals this novel support's ani-poisoning effect. Besides, it shows the Tafel slope of 26 mV dec⁻¹ and overpotentials of 47 and 131 mV were obtained at 10 and 100 mA cm⁻² in acidic media toward HER. Exploring and designing new electrocatalysts may be enhanced by this research, which can use Hemin as a novel support for noble metals such as Pt, Pd, Rh, Au, and Ru for diverse energy-related applications.     

Nanocrystaline tungsten carbide supported Au–Pd electrocatalyst for oxygen reduction

Au–Pd nanobimetallic particles supported on nanocrystaline tungsten carbide as electrocatalysts for oxygen reduction were prepared by an intermittent microwave heating (IMH) method. XRD measurement revealed that AuPd alloy formed during the IMH process. We showed these novel electrocatalysts could offer the activities that surpass that of the state-of-the-art Pt-based electrocatalysts for oxygen reduction reaction. The AuPd–WC/C electrode showed an over 70 mV shift towards more positive potentials compared to Pt/C electrode for ORR. The advantage seemed to come from the novel support of tungsten carbide which itself has the catalytic activity to enhance the catalytic activity of the metal electrocatalysts.