Particle shape control using pulse electrodeposition: Methanol oxidation as a probe reaction on Pt dendrites and cubes

Shape controlled Pt particles were synthesized onto tungsten monocarbide (WC) substrates using a pulse electrodeposition method. The particle shape was strongly influenced by the deposition potential, with cubic particles formed using 0.14 V vs. NHE (normal hydrogen electrode) and dendritic particles formed at 0.04 V vs. NHE. The crystalline orientation and active surface area of the Pt particles were estimated using Cu stripping voltammetry. Finally, cyclic voltammetry and chronoamperometry were used to determine the methanol electrooxidation activity, which revealed that the dendritic Pt showed much higher electrochemical activity than the cubic particles. These results demonstrated the possibility of more effectively utilizing Pt electrocatalysts by controlling the shape of Pt particles.     

Nanostructured platinum catalyst layer prepared by pulsed electrodeposition for use in PEM fuel cells

Nanostructured thin catalyst layer with uniform distribution of platinum particles on a GDL useful for PEM fuel cell was obtained by preferential pulsed electrodeposition (PED) from a dilute solution of chloroplatinic acid. A low platinum loading on the electrode was obtained by PED method, without any loss in fuel cell performance compared with electrodes prepared by conventional brush coating method. The electrodeposition was optimized by varying the duty cycle and current density. The fuel cell performance was found to be 350 mA/cm² at an operating voltage of 0.6 V at 60 °C with hydrogen and air as reactants at ambient pressure. The nanostructured thin catalyst layer showed a very less ohmic resistance of 0.00076 mΩ/cm².     

Excellent electrocatalysis of methanol oxidation on platinum nanoparticles supported on carbon-coated silicon

The prepared carbon-coated silicon (Si@C) material was blended with graphite powder together to form the specific carbon paste electrode with different mass percent X% of Si@C (CPE-Si@C(X%)). The electrochemical impedance spectroscopy (EIS) was performed on the prepared CPE-Si@C and the pure carbon paste electrode (CPE), and the results show that the CPE-Si@C (X%) electrode has a smaller charge transfer resistance. Pt/CPE and Pt/CPE-Si@C(X%) electrodes were prepared by electrodepositing Pt particles on CPE-Si@C and CPE, and the obtained electrodes were used for electrocatalytic oxidation of methanol in acid media. The results show that the activity of Pt/CPE-Si@C(X%) electrode for electrocatalytic oxidation of methanol was higher than that of Pt/CPE electrode, and the mass peak current density of Pt/CPE-Si@C(10%) electrode for electrocatalytic oxidation of methanol reached 321 mA mg^?1, which was 1.8 times higher than that of Pt/CPE electrode. The Pt/CPE-Si@C (10%) electrode and the Pt/CPE electrode were characterized by chronoamperometry. The results show that Pt/CPE-Si@C (10%) has a better stability of activity and stronger tolerance against CO poisoning.     

Preparation and activity of carbon-supported porous platinum as electrocatalyst for methanol oxidation

In this paper, we reported a novel electrocatalyst, Vulcan XC-72-supported porous platinum nano-particles (Pt_p/C) for methanol oxidation. In the preparation of Pt_p/C, platinum precursor was first adsorbed on carbon and then reduced by l-ascorbic acid in ethylene glycol solution. The structure and morphology of Pt_p/C and its activity toward methanol oxidation were characterized by transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) measurement, X-ray diffraction (XRD), energy-dispersion spectrometer (EDS), cyclic voltammetry (CV), and chronoamperometry (CA), with a comparison of the electrocatalyst prepared with sodium borohydride as reducer (Pt_s/C). It is found that both electrocatalysts have similar particle size but have different surface morphology of platinum and thus exhibit different electrocatalytic activity toward methanol oxidation. The platinum particle size of both electrocatalysts is 3–5 nm, but the corresponding BET surface areas are different significantly, 131.6 m² g⁻¹ and 87.7 m² g⁻¹ for Pt_p/C and Pt_s/C, respectively, indicative of the porous structure of platinum particles in Pt_p/C. The peak current for methanol oxidation on CV is 167 mA mg⁻¹ and 44 mA mg⁻¹ for Pt_p/C and Pt_s/C, respectively, indicative of the high electrocataytic activity of Pt_p/C toward methanol oxidation. The result from CA shows that Pt_p/C has good stability as the electrocatalyst for methanol oxidation.     

Carbon nanotube supported Pt electrodes for methanol oxidation: A comparison between multi- and single-walled carbon nanotubes

This work presents a detailed comparison between multi-walled (MWNT) and single-walled carbon nanotubes (SWNT) in an effort to understand which can be the better candidate of a future supporting carbon material for electrocatalyst in direct methanol fuel cells (DMFC). Pt particles were deposited via electrodeposition on MWNT/Nafion and SWNT/Nafion electrodes to investigate effects of the carbon materials on the physical and electrochemical properties of Pt catalyst. The crystalloid structure, texture (surface area, pore size distribution, and macroscopic morphology), and surface functional groups for MWNT and SWNT were studied using XRD, BET, SEM and XPS techniques. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the electrochemically accessible surface area and charge transfer resistances of the MWNT/Nafion and SWNT/Nafion electrodes. CO stripping voltammograms showed that the onset and peak potentials on Pt-SWNT/Nafion were significantly lower that those on the Pt-MWNT/Nafion catalyst, revealing a higher tolerance to CO poisoning of Pt in Pt-SWNT/Nafion. In methanol electrooxidation reaction, Pt-SWNT/Nafion catalyst was characterized by a significantly higher current density, lower onset potentials and lower charge transfer resistances using CV and EIS analysis. Therefore, SWNT presents many advantages over MWNT and would emerge as an interesting supporting carbon material for fuel cell electrocatalysts. The enhanced electrocatalytic properties were discussed based on the higher utilization and activation of Pt metal on SWNT/Nafion electrode. The remarkable benefits from SWNT were further explained by its higher electrochemically accessible area and easier charge transfer at the electrode/electrolyte interface due to SWNT's sound graphitic crystallinity, richness in oxygen-containing surface functional groups and highly mesoporous 3D structure.     

Na-intercalated carbon nanotubes-supported platinum nanoparticles as new highly effective catalysts for preferential CO oxidation in H2-rich stream

Na⁺-intercalated carbon nanotubes (Na-CNTs) were obtained by impregnation of CNTs with sodium acetate followed by annealing at high temperatures under argon. Stable Na-CNTs-supported Pt catalysts (Pt/Na-CNT catalysts) were then prepared for hydrogen purification via preferential CO oxidation in a H₂-rich stream (CO-PROX). Characteristic studies show that the content of Na⁺ species in CNTs is increased with increased annealing temperature and the Pt nanoparticles with an average size of 2–3 nm are uniformly dispersed on the surfaces of Na-CNTs. An optimized Pt/Na-CNT catalyst with 5 wt% Pt loading can completely remove CO from 40 °C to 200 °C. This catalyst also exhibits long-term stability for 1000 h at 100 °C in feed gas containing 1% CO, 1% O₂, 50% H₂, 15% CO₂, and 10% H₂O balanced with N₂. The electron transfer between the Pt nanoparticles and Na⁺ species plays an important role in enhancing the CO-PROX performance of the catalyst.     

Comparison of methanol and ethylene glycol oxidation by alloy and Core-Shell platinum based catalysts

Two Core-Shell, Ru_Core-Pt_Shell and IrNi_Core-PtRu_Shell, XC72-supported catalyst were synthesized in a two-step deposition process with NaBH₄ as reducing agent. The structure and composition of the Core-Shell catalysts were determined by EDS, XPS and XRD. Electrochemical characterization was performed with the use of cyclic voltammetry. Methanol and ethylene glycol oxidation activities of the Core-Shell catalysts (in terms of surface and mass activities) were studied at 80 °C and compared to those of a commercial Pt-Ru alloy catalyst. The surface activity of the alloy based catalyst, in the case of methanol oxidation, was found to be superior as a result of optimized surface Pt:Ru composition. However, the mass activity of the PtRu/IrNi/XC72 was higher than that of the alloy based catalyst by ∼50%. Regarding ethylene glycol oxidation, while the surface activity of the alloy based catalyst was slightly higher than that of the Pt/Ru/XC72 catalyst, the latter showed ∼66% higher activities in terms of A g⁻¹ of Pt. These results show the potential of Core-Shell catalysts for reducing the cost of catalysts for DMFC and DEGFC.     

Pt electrodeposited on CeZrO4/MCNT as a new alternative catalyst for enhancement of ethanol oxidation

Electrocatalytic preparation of Pt-based nanocomposites has been investigated for improvement of direct ethanol fuel cells (DEFCs). In this study, new alternative catalysts of Pt-decorated cerium zirconium oxide-modified multiwalled carbon nanotubes (Pt/CeZrO₄/MCNT) were successively prepared to improve the activity of the ethanol oxidation reaction (EOR). The prepared CeZrO₄ with a face-centered cubic (fcc) structure compatibly dispersed onto MCNT provides abundant active Pt sites for highly active catalysts. The fcc-structured Pt was also satisfactorily decorated onto CeZrO₄/MCNT, resulting in highly active Pt. The Ce⁴⁺/Ce³⁺ redox property can promote oxygen vacancies to improve the electrochemical activity for oxidation of carbonaceous species. An increase in roughness and a stabilized catalyst structure can also be produced by inserting Zr⁴⁺ into the ceria metal oxide. The prepared Pt/20%CeZrO₄/MCNT catalysts present excellent electrochemical active surface area, mass activity, CO tolerance and high electron kinetic transfer with low resistance and high stability over commercial PtRu/C toward EOR. This promising catalyst material could be introduced to enhance the anodic oxidation reaction in DEFCs.     

Synthesis and characterization of Pt nanoparticles on sulfur-modified carbon nanotubes for methanol oxidation

Pt nanoparticles supported on carbon nanotubes (Pt/CNTs) have been synthesized from sulfur-modified CNTs impregnated with H₂PtCl₆ as Pt precursor. The dispersion and size of Pt nanoparticles in the synthesized Pt/CNT nanocomposites are remarkably affected by the amount of sulfur modifier (S/CNT ratio). The results of X-ray diffraction and transmission electron microscopy indicate that an S/CNT ratio of 0.3 affords well dispersed Pt nanoparticles on CNTs with an average particle size of less than 3 nm and a narrow size distribution. Among different catalysts, the Pt/CNT nanocomposite synthesized at S/CNT ratio of 0.3 showed highest electrochemically active surface area (88.4 m² g⁻¹) and highest catalytic activity for methanol oxidation reaction. The mass-normalized methanol oxidation peak current observed for this catalyst (862.8 A g⁻¹) was ∼ 6.5 folds of that for Pt deposited on pristine CNTs (133.2 A g⁻¹) and ∼ 2.3 folds of a commercial Pt/C (381.2 A g⁻¹). The results clearly demonstrate the effectiveness of a relatively simple route for preparation of sulfur-modified CNTs as a precursor for the synthesis of Pt/CNTs, without the need for tedious pretreatment procedures to modify CNTs or complex equipments to achieve high dispersion of Pt nanoparticles on the support.     

HxMoO3-assisted deposition of platinum nanoparticles on MWNTs for electrocatalytic oxidation of methanol

Platinum nanoparticles were loaded on multi-walled carbon nanotubes (MWNTs) by using ethylene glycol as reductant and with the assistance of hydrogen molybdenum bronze (H_xMoO₃, 0 < x ≤ 2) for the electrocatalytic oxidation of methanol. In this approach, MWNTs were modified by H_xMoO₃ and used as the support for platinum nanoparticles. The XRD and TEM characterizations indicate that the average particle size of platinum supported by the modified MWNTs (Pt/H_xMoO₃-modified-MWNTs) is 3.4 nm, smaller than that (4.3 nm) of the platinum supported by the unmodified MWNTs (Pt/MWNTs). The voltammetric and chronoamperometric experiments show that Pt/H_xMoO₃-modified-MWNTs exhibits better electrocatalytic activity toward methanol oxidation than Pt/MWNTs, although the former has a less platinum loading (4.6 wt%) than the latter (6.0 wt%). The mechanism on the assistance of H_xMoO₃ to the platinum deposition was discussed.     

Oxygen reduction catalytic ability of platinum nanoparticles prepared by room-temperature ionic liquid-sputtering method

Pt nanoparticles can be produced by a Pt sputtering method onto trimethyl-n-propylammonium bis((trifluoromethyl)sulfonyl)amide (Me₃PrNTf₂N) room-temperature ionic liquid (RTIL) without stabilizing agents. Pt nanoparticles obtained by the Pt sputtering method showed mean particle size of ca. 2.3-2.4 nm independently of sputtering time. A Pt-embedded glassy carbon electrode (Pt-GCE) consisting of the Pt-sputtered RTIL and a glassy carbon plate showed a favorable catalytic activity to oxygen reduction reaction. The catalytic ability was enhanced by Me₃PrNTf₂N modification of the Pt-GCE. In addition, carbon monoxide never absorbed onto the RTIL-modified Pt-GCE.     

Platinum decorated Ru/C: Effects of decorated platinum on catalyst structure and performance for the methanol oxidation reaction

Platinum decorated Ru/C catalysts are prepared by successive reduction of a platinum precursor on pre-formed Ru/C. Pt:Ru atomic ratios are varied from 0.13:1 to 0.81:1 to investigate the platinum decoration effects on the catalyst's structure and electrochemical performance towards the methanol oxidation reaction (MOR) at room temperature. The catalysts are extensively characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Ru@Pt/C catalysts show enhanced mass-normalized activity and specific activity for the MOR relative to Pt/C. For the anodic oxidation of methanol, the ratio of forward to reverse oxidation peak current R (I_f/I_b) varies considerably: R decreases from 5.8 to 0.8 when the Pt:Ru ratio increases from 0.13:1 to 0.81:1. When the ratio of Pt:Ru is 0.42:1, R reaches 0.99 (close to that of Pt/C), and further increase of the Pt:Ru ratio leads to almost no decrease in R. Coincidentally, maximum mass-normalized activity is also obtained when Pt:Ru is 0.42:1.     

High-efficiency carbon-supported platinum catalysts stabilized with sodium citrate for methanol oxidation

A high-efficiency platinum catalyst stabilized with sodium citrate for methanol oxidation is introduced in this paper, in which freshly prepared non-noble active cobalt is employed as reducer. According to X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements, the novel as-prepared nanoclusters Pt catalyst dispersed on carbon is composed of Pt nanoparticles, and the average particle size of the Pt nanoparticles is 2.0 nm. The catalyst with sodium citrate shows a very high electrochemically active surface area and significant increase electrocatalytic activity towards methanol oxidation, which indicates that it would be a better potential candidate for application in a direct methanol fuel cell (DMFC).     

Characterization and single cell testing of Pt/C electrodes prepared by electrodeposition

Electrodes for proton exchange membrane fuel cells (PEMFC) have been prepared by the electrodeposition method. For this task, the electrodeposition of platinum is carried out on a carbon black substrate impregnated with an ionomer, proton conducting, medium. Before electrodeposition, the substrate is submitted to an activation process to increase the hydrophilic character of the surface to a few microns depth.Electrodeposition of platinum takes place inside the generated surface hydrophilic layer, resulting in a continuous phase covering totally or partially carbon substrate grains. Cross sectional images show a decay profile of platinum towards the interior of the substrate, reflecting a deposition process limited by diffusion of PtCl₆²⁻ through the porous substrate. Electrodes with different platinum loads have been prepared, and membrane electrode assemblies (MEA) have been mounted with the electrodeposited electrodes as cathode and other standard components (commercial anode and Nafion^R 117 membrane). The electrochemically active surface area determined from hydrogen underpotential deposition charge, is lower on the electrodeposited electrodes than on standard electrodes. However, single cell testing shows higher mass specific activity on electrodeposited cathodes with low and intermediate Pt load (below 0.05 mg Pt cm⁻²).     

Synthesis and electrocatalysis of 1-aminopyrene-functionalized carbon nanofiber-supported platinum-ruthenium nanoparticles

Platinum-ruthenium/carbon composite nanofibers were prepared by depositing PtRu nanoparticles directly onto electrospun carbon nanofibers using a polyol processing technique. The morphology and size of PtRu nanoparticles were controlled by 1-aminopyrene functionalization. The noncovalent functionalization of carbon nanofibers by 1-aminopyrene is simple and can be carried out at ambient temperature without damaging the integrity and electronic structure of carbon nanofibers. The resulting PtRu/carbon composite nanofibers were characterized by cyclic voltammogram in 0.5 M H₂SO₄ and 0.125 M CH₃OH + 0.2 M H₂SO₄ solutions, respectively. The PtRu/carbon composite nanofibers with 1-aminopyrene functionalization have smaller nanoparticles and a more uniform distribution, compared with those pretreated with conventional acids. Moreover, PtRu/1-aminopyrene functionalized carbon nanofibers have high active surface area and improved performance towards the electrocatalytic oxidation of methanol.     

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).     

Electrodeposition of platinum microparticle interface on conducting polymer film modified nichrome for electrocatalytic oxidation of methanol

A simple and “green” approach for fabrication of platinum microparticle interface on conducting polymer film modified nichrome matrix (Pt/PAn/Nc) for methanol oxidation was investigated. The Pt microparticles were grown directly on the polyaniline precursor film modified nichrome matrix (PAn/Nc) in dilute chloroplatinic acid solution by cyclic voltammetry. The SEM revealed that the deposits were composed of spherical Pt microparticles. Cyclic voltammetry and chronoamperometry were used for characterization of the electrode properties. Results showed that the spherical Pt/PAn/Nc electrode enhanced the catalytic activity and promoted methanol electrooxidation. The catalytic activity of Pt/PAn/Nc electrode was 15 times higher than that obtained from pure platinum under the same conditions. Moreover, the deposited Pt microparticles improved the electrochemical properties of nichrome and reduced the dosage of noble metal platinum, remarkably. The cost could be reduced dramatically by decreasing the contents of platinum. The Pt/PAn/Nc are likely a promising electrocatalyst for methanol electrooxidation.     

Carbon nanotube-supported Pt-HxMoO3 as electrocatalyst for methanol oxidation

Carbon nanotube (CNT)-supported platinum modified with H_xMoO₃ (Pt-H_xMoO₃/CNT) was prepared and used as an electrocatalyst for methanol oxidation. In the preparation of this electrocatalyst, a platinum precursor was loaded on CNTs and reduced by sodium borohydride in ethylene glycol, resulting in CNT-supported platinum without modification (Pt/CNT), and then the Pt/CNT was modified with H_xMoO₃ that was formed by hydrolysis and subsequent reduction of ammonium molybdate. The surface morphology, structure and composition of Pt-H_xMoO₃/CNT and Pt/CNT as well as their activity toward methanol oxidation were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), chronoamperometry (CA), chronopentiometry (CP), and electrochemical impedance spectroscopy (EIS). The results, obtained from TEM, XRD, EDS, and FTIR, indicate that the platinum loaded on CNTs has a face-centered cubic structure with particle sizes of 2–5 nm, and the modification of H_xMoO₃ on platinum with an atom ratio of Pt:Mo = 2:1 has little effect on the particle size, distribution and structure of the platinum. The results, obtained from CV, CA, CP, and EIS, show that the Pt-H_xMoO₃/CNT exhibits higher electrocatalytic activity toward methanol oxidation and better carbon monoxide tolerance than Pt/CNT.     

Platinum nanoparticles supported on activated carbon fiber as catalyst for methanol oxidation

Activated carbon fiber (ACF) with high specific surface area has been used as support in the preparation of Pt nanoparticles electrocatalyst (Pt/ACF) for direct alcohol fuel cells. It is found that the Pt nanoparticles on ACF are highly and homogeneously dispersed with a narrow size distribution in the range of 1.5–3.5 nm with an average size of 2.4 nm. In comparison with the commercial E-TEK Pt/C catalyst, the Pt/ACF catalyst exhibits much higher catalytic activity for methanol, ethanol and isopropanol oxidation, which are about 2.4 times as high as that of the former. The Pt/ACF catalyst is observed to be significantly more stable during the constant current density polarization and continuous cyclic voltammetry in comparison with Pt/C catalyst. Both the uniform dispersion of Pt nanoparticles and strong interactions between Pt nanoparticles and ACF are of benefit to achieve the performance improvement of Pt/ACF catalyst.     

Effect of noble metal species and compositions on manganese dioxide-modified carbon nanotubes for enhancement of alcohol oxidation

By integrating the effects of alloying, chemical composition and support, a series of mono- and bi-metallic catalyst nanoparticles electrodeposited on α-manganese dioxide (MnO₂)-modified carbon nanotube (CNT) supports were synthesized to improve the efficiency of direct alcohol fuel cells. Small and dispersed nanoparticles on the CNT/MnO₂ surfaces with high electrochemically active surface area (ECSA) were successfully obtained in this work. The support materials were characterized by Fourier-transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD), while the as-prepared catalysts were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) and chronoamperometry (CA) were used to study the activity and stability of the catalysts, respectively. The results showed that a combination of Pt, Pd, Au and MnO₂ on the CNTs significantly affected the topography of the composite catalyst surfaces, and their electrochemical measurements showed excellent electrocatalytic activity toward the reaction. For methanol and ethanol oxidation in acid solution, CNT/MnO₂/1M3Pt (M = Pd or Au) catalysts revealed greater activity improvement compared to the other prepared catalysts. For the bimetallic CNT/MnO₂/xMyPt catalysts, the values of the forward peak current (I_f)) and the ratio of the forward peak current to the reverse peak current (I_f/I_b) were higher, while their onset potentials (E_o) were lower compared to those of the monometallic CNT/MnO₂/4Pt catalyst. Moreover, CO oxidation on these bimetallic catalysts was also confirmed to be poisoning resistant. These results indicate that our prepared catalyst showed excellent electrocatalytic performance, reliability, and stability. The catalytic activity improvement was based upon the unique integrated structural and functional properties and the synergistic effect of different compositions in the catalyst system.