Pt-Ni alloy nanoparticles supported on CNF as catalyst for direct ethanol fuel cells

Carbon nanofiber (CNF) network supported Pt and Pt-Ni alloy nano particle catalysts were prepared by electrochemical deposition at different deposition cycles. Structure, composition and surface morphology of the Pt/CNF and Pt-Ni/CNF were analyzed using X-ray diffraction, Energy dispersive X-ray spectroscopy and field emission scanning electron microscopy. Structural analysis by XRD revealed a face centered cubic crystal structure for Pt and its alloy. SEM images have shown that the Pt-Ni nanoparticles distributed evenly on the CNF network. The electrocatalytic activity of the Pt/CNF and Pt-Ni/CNF electrodes was verified using an electrochemical linear voltammetrty (ELV), cyclic voltammetry (ECV) and electrochemical impedance spectroscopy (EIS) in an alkaline solution containing 1 M C₂H₅OH + 1 M KOH. The results show increased catalytic activity with enhancement of the Pt-Ni alloy formation.     

Electro-oxidation of ethanol using PtRuBi/C electrocatalyst prepared by borohydride reduction

Pt/C, PtRu/C, PtBi/C, and PtRuBi/C electrocatalysts (20 wt.% metal loading) were prepared by borohydride reduction using H₂PtCl₆·6H₂O, RuCl₃·xH₂O, and Bi(NO₃)₃·5H₂O as metal sources and Vulcan XC 72 as support. The electrocatalysts were characterized by energy-dispersive X-ray analysis, X-ray diffraction, and thermogravimetric analysis. The electro-oxidation of ethanol was studied in sulfuric acid solution by cyclic voltammetry and chronoamperometry. The electrochemical studies showed that PtRuBi/C (50:40:10) electrocatalyst has superior performance for ethanol electro-oxidation at room temperature compared to the other electrocatalysts. Preliminary tests at 100 °C on a single direct ethanol fuel cell also confirm the results obtained by electrochemical techniques.     

Exploration of bimetallic Pt-Pd/C nanoparticles as an electrocatalyst for oxygen reduction reaction

In this study, carbon supported Pt and Pt-Pd were synthesized as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs). Pt and Pt-Pd nanoparticles have been synthesized by reduction of metal precursors in presence of NaBH₄. Various techniques such as X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) were utilized to study the prepared samples. Furthermore, electrochemical properties of the prepared samples were evaluated from cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The results showed, the crystallite size of electrocatalysts (Pt and Pt-Pd) is below 10 nm. The higher catalytic activity was detected for Pt-Pd/C electrocatalyst for oxygen reduction reaction (ORR). In addition, it is believed that the better performance of electrocatalyst is related to the synergic effect between Pt and Pd nanoparticles, weakening of the OO bond on Pd-modified Pt nanoparticles in ORR, uniform dispersion of Pd and Pt on the carbon support and higher electrochemical active surface area (EAS) of Pt-Pd/C electrocatalyst.     

A comparative study for the electrocatalytic oxidation of alcohol on Pt-Au nanoparticle-supported copolymer-grafted graphene oxide composite for fuel cell application

The platinum-gold bimetallic nanoparticles supported poly(cyclotriphosphazene-co-benzidine)-grafted graphene oxide (poly(CP-co-BZ)-g-GO) composite has been prepared for electrochemical performance studies. Cyclic voltammetry and chronoamperometric studies were carried out to check the electrochemical properties of Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO catalysts for methanol, ethylene glycol and glycerol in alkaline medium. The morphology and crystalline structure of the prepared Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO and catalysts have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). From the electrochemical results, it was concluded that Pt-Au/poly(CP-co-BZ)-g-GO catalyst shows higher catalytic activity and stability compared to Pt/poly(CP-co-BZ)-g-GO catalyst. The catalytic activity of Pt/poly(CP-co-BZ)-g-GO catalyst has been compared with Pt/poly(CP-co-BZ), Pt/GO and Pt/C catalysts. In addition, oxidation current of ethylene glycol is higher than the methanol and glycerol in alkaline medium on the prepared catalyst.     

PtRu/carbon hybrid materials prepared by hydrothermal carbonization as electrocatalysts for methanol electrooxidation

PtRu/carbon hybrid materials were prepared by hydrothermal carbonization using starch as carbon source and reducing agent and H₂PtCl₆.6H₂O and RuCl₃.xH₂O as metal sources of the carbonization process. The materials were prepared in the following conditions: without pH adjustment, in the absence and in the presence of tetrapropylammonium chloride, and adjusting the pH using potassium hydroxide or tetrapropylammonium hydroxide. The as-synthesized materials were further treated under argon atmosphere at 900 °C and characterized by energy dispersive X-ray spectroscopy, thermogravimetric analysis, BET isotherm, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscope, and cyclic voltammetry. The electrooxidation of methanol was studied by chronoamperometry. The addition of tetrapropylammonium ion promoted an increase in surface area and total pore volume while the alkaline medium favored smaller particle sizes. The material prepared using tetrapropylammonium hydroxide showed the best electroactivity for methanol electrooxidation compared to others obtained materials.     

Surface composition of ordered intermetallic compounds PtBi and PtPb

The surface composition of bulk electrodes made from the ordered intermetallic phases PtBi and PtPb has been studied by ex-situ X-ray photoelectron spectroscopy (XPS) after being subjected to various electrochemical treatments. Analysis of the freshly polished surfaces showed that in the surface and near surface regions the less-noble metals; Bi and Pb are oxidized to a significant extent (28% and 41%, respectively). Upon cycling to increasingly positive potentials, the fraction of oxidized to metallic forms of Bi and Pb decreased gradually to reach the minimal values of 7% and 6% at +400 mV vs. Ag/AgCl (saturated KCl). The observed decrements are due to leaching of surface oxides; Bi₂O₃ on PtBi and PbCO₃ or Pb(OH)₂ on PtPb. When the potential sweep was extended to more positive values, there was a linear decrease in the surface concentration of the less-noble metal, along with a slight increase in the amount of the species in their oxidized state (Bi₂O₃ for PtBi and PbSO₄ for PtPb). Leaching of Bi from the electrode surface occurs in accordance to the Pourbaix diagram for elemental bismuth, indicating no significant increase in stability arising from the formation of an intermetallic phase with platinum. In the case of PtPb, however, the Pb starts to dissolve away at potentials significantly more positive (+800 mV) than what was anticipated from the Pourbaix diagram. The results obtained here are in accord with our previous observations on the effects of electrochemical pre-treatment on these intermetallic phases for the electrocatalytic oxidation of formic acid and other potential fuel cell fuels.     

ZnO-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material for lithium-ion batteries synthesized by a combustion method

ZnO-coated LiMn₂O₄ cathode materials were prepared by a combustion method using glucose as fuel. The phase structures, size of particles, morphology, and electrochemical performance of pristine and ZnO-coated LiMn₂O₄ powders are studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge test, and X-ray photoelectron spectroscopy (XPS). XRD patterns indicated that surface-modified ZnO have no obvious effect on the bulk structure of the LiMn₂O₄. TEM and XPS proved ZnO formation on the surface of the LiMn₂O₄ particles. Galvanostatic charge/discharge test and rate performance showed that the ZnO coating could improve the capacity and cycling performance of LiMn₂O₄. The 2 wt% ZnO-coated LiMn₂O₄ sample exhibited an initial discharge capacity of 112.8 mAh g^?1 with a capacity retention of 84.1 % after 500 cycles at 0.5 C. Besides, a good rate capability at different current densities from 0.5 to 5.0 C can be acquired. CV and EIS measurements showed that the ZnO coating effectively reduced the impacts of polarization and charge transfer resistance upon cycling.     

Nanoparticulate TiO2-promoted PtRu/C catalyst for methanol oxidation

To improve the electrocatalytic properties of PtRu/C in methanol electrooxidation, nanoparticulate TiO₂-promoted PtRu/C catalysts were prepared by directly mixing TiO₂ nanoparticles with PtRu/C. Using cyclic voltammetry, it was found that the addition of 10 wt% TiO₂ nanoparticles can effectively improve the electrocatalytic activity and stability of the catalyst during methanol electrooxidation. The value of the apparent activation energy (E _a) for TiO₂-PtRu/C was lower than that for pure PtRu/C at a potential range from 0.45 to 0.60 V. A synergistic effect between PtRu and TiO₂ nanoparticles is likely to facilitate the removal of CO-like intermediates from the surface of PtRu catalyst and reduce the poisoning of the PtRu catalysts during methanol electrooxidation. Therefore, we conclude that the direct introduction of TiO₂ nanoparticles into PtRu/C catalysts offers an improved facile method to enhance the electrocatalytic performance of PtRu/C catalyst in methanol electrooxidation.     

Electrooxidation of ethanol using Pt rare earth–C electrocatalysts prepared by an alcohol reduction process

Pt rare earth–C electrocatalysts (rare earth = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Lu) were prepared by an alcohol reduction process using ethylene glycol as reduction agent and solvent and Vulcan XC 72 as support. The electrocatalysts were characterized by energy-dispersive X-ray analysis, X-ray diffraction (XRD), and cyclic voltammetry. The electrooxidation of ethanol was studied in acid medium by cyclic voltammetry and chronoamperometry using thin porous coating technique. The XRD patterns indicate that all electrocatalysts present the face-centered cubic structure of Pt and the presence of rare earth hydroxides. All electrocatalysts prepared by this methodology showed superior performance for ethanol electrooxidation at room temperature compared to Pt–C.     

Flowerlike PtCl4/Bi2WO6 composite photocatalyst with enhanced visible-light-induced photocatalytic activity

Flowerlike PtCl₄/Bi₂WO₆ composite photocatalyst was successfully synthesized through a simple two-step method involving a template-free hydrothermal process and the following impregnation treatment. The samples were fully characterized by the study of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis absorption spectra. The results indicated that the doping of Pt species did not affect the crystal structure and the morphology of Bi₂WO₆ photocatalyst, but it had great influences on the photocatalytic activity of Bi₂WO₆ towards rhodamine-B (RhB) degradation. Besides, the Pt species was found to be present as PtCl₄ in the composite samples, and also an optimal Pt species content on the surface of Bi₂WO₆ photocatalyst was discovered with the highest photocatalytic ability. The improved photocatalytic performance could be ascribed to the enhanced interfacial charge transfer and the inhibited recombination of electron-hole pairs. Meanwhile, a possible mechanism for RhB photocatalytic degradation over PtCl₄/Bi₂WO₆ catalyst was also proposed.     

Fuel cell and electrochemical studies of the ethanol electro-oxidation in alkaline media using PtAuIr/C as anodes

Ethanol electro-oxidation reaction was investigated considering conventional electrochemical experiments in alkaline media, direct ethanol fuel cell (DEFC), and in situ ATR-FTIR. The working electrode/anodes were composed of monometallic Pt/C, Au/C, Ir/C, and trimetallic PtAuIr/C nanoparticles with atomic Pt/Au/Ir ratios of 40:50:10, 50:40:10, 60:30:10, 70:20:10, and 80:10:10. X-ray diffraction (XRD) suggests PtAuIr/C alloy formation, and according to transmission electron micrographs, the mean particle sizes are from 4 to 6 nm for all catalyst compositions. PtAuIr/C 40:50:10 showed the highest catalytic activity for ethanol electro-oxidation in the electrochemical experiments; using this material, the peak current density from ethanol electro-oxidation on cyclic voltammetry experiment was 50 mA per g of Pt, 3.5 times higher than that observed with Pt/C. The fuel cell performance was superior using all PtAuIr/C compositions than using Pt/C. Au/C and Ir/C presented very poor catalytic activity toward ethanol electro-oxidation. The improved results obtained using PtAuIr/C might be related to the OH_ads species formed at low overpotential on Ir and to the decrease on adsorption energy of poisoning intermediates on Pt sites, promoted by Au.     

Synthesis and electrochemical performance of α-nickel hydroxide codoped with Al3+ and Ca2+

α-Nickel hydroxide codoped with Al³⁺ and Ca²⁺ was prepared by chemical coprecipitation method. The phase structure and surface morphology of the prepared samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical performances of the prepared samples were analyzed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. XRD and SEM tests reveal that the Al³⁺/Ca²⁺ codoped α-nickel hydroxide has a relatively good crystallization and a very coarse surface. Electrochemical tests show that the Al³⁺/Ca²⁺ codoped α-nickel hydroxide has higher proton diffusion coefficient, lower electrochemical reaction resistance, and higher discharge capacity (395.3 mAh g^?1 at 0.2 C) than the Al³⁺ singly doped α-nickel hydroxide, which indicates its potential application as an electrode material for secondary alkaline batteries.     

An X-ray photoelectron spectroscopy investigation of a novel Pd–Pt colloid catalyst

A Bi-promoted charcoal-supported Pd–Pt oxidation catalyst prepared from colloidal NOct₄Cl-stabilized Pd–Pt nanoparticles was investigated by means of X-ray photoelectron spectroscopy (XPS). Pd 3d, Pt 4f, Bi 4f, C 1s and O 1s spectra of the colloid, the supported colloid catalyst and a conventional charcoal-supported Pd–Pt/Bi coimpregnation catalyst (Degussa, CEF 196 RA/W) were measured. Both catalysts were explored unused (as-prepared) and after deactivation in the heterogeneous catalytic oxidation of glucose to gluconic acid. The spectra are analyzed to elucidate the higher starting activity of the Pd–Pt/Bi/C colloid catalyst, especially the role of the promotor Bi and the mechanisms leading to catalyst deactivation. The higher starting activity of the colloid catalyst is explained by the presence of completely reduced Pd and Pt, threevalent Bi and a smaller particle size in contrast to the conventional catalyst which contains partly oxidized Pd and a non-unique chemical state of Bi. The deactivation of both catalysts is suggested to be due to metal dissolution, particle growth and chemical poisoning.     

Synthesis and characterization of highly textured Pt–Bi thin films

Pt–Bi films were synthesized on glass and thermally oxidized silicon substrates by e-beam evaporation and annealing. The structures were characterized using X-ray diffraction (XRD) and transmission electron microscopy/selected area electron diffraction (TEM/SAED) techniques. Single-phase PtBi was obtained at an annealing temperature of 300°C, whereas a higher annealing temperature of 400°C was required to obtain the highly textured γ-PtBi₂ phase. TEM/SAED analysis showed that the films annealed at 400°C contain a dominant γ-PtBi₂ phase with a small amount of β-PtBi₂ and α-PtBi₂ phases. Both the PtBi and γ-PtBi₂ phases are highly textured in these two kinds of film: the c-axis of the hexagonal PtBi phase is mostly in the film plane, whereas the c-axis of the trigonal γ-PtBi₂ phase is perpendicular to the film plane. The electrical resistivity of the film with the γ-PtBi₂ phase was smaller by one order of magnitude than that of the film with the PtBi phase.     

Novel synthesis and characterization of nanocomposite Pt-WO3-TiO2/C electrocatalyst for PEMFC

In this study, an effective preparation of Pt-WO₃-TiO₂/C electrocatalysts has been developed for polymer electrolyte membrane fuel cell (PEMFC) application. The single cell performance of Vulcan XC-72R carbon-supported Pt-WO₃-TiO₂ electrocatalysts with various compositions (as weight percentage Pt-W-Ti 0:5:5, 2:4:4, 4:3:3, 6:2:2, and 8:1:1) as anode materials are investigated in PEMFC. These catalysts are compared with 10 % Pt/C on the same Vulcan XC-72R carbon support and 10 % Pt/C (commercial) electrocatalyst. The physical and morphological characterization of the optimized Pt-WO₃-TiO₂/C, 10 % Pt/C, and 10 % Pt/C (commercial) electrocatalysts are further investigated by X-ray diffraction (XRD), cyclic voltammetry, scanning electron microscopy with energy-dispersive X-ray analysis, and transmission electron microscopy (TEM) techniques. Among all the molar ratio of the catalysts, the Pt-W-Ti (4:3:3) molar ratio catalyst exhibited the larger electrochemical active surface area. The electrochemical performance of Pt-WO₃-TiO₂/C (with a weight percentage of Pt-W-Ti 4:3:3) as anode material is better than those of other compositions of Pt-WO₃-TiO₂/C catalysts. The amount of platinum was also reduced from 1.76 to 0.704 mg cm^?2 which exhibited higher performance in single cell tests. Platinum shows a smaller-sized crystalline structure in XRD and TEM analysis. High performance indicates that enhanced proton transport occurs through the use of this catalyst.     

An effective electrocatalyst for ethanol oxidation: Pt-modified IrCu alloy nanoparticle

There is a growing interest in ethanol oxidation electrochemistry as it plays an important role in renewable energy technologies. The goal of this work was to develop active multifunctional catalyst materials for ethanol oxidation. Here, a carbon-supported Pt-modified IrCu alloy electrocatalyst (Pt–IrCu/C) was prepared by a two-step method. X-ray diffraction and transmission electron microscope showed that the Pt–IrCu/C has a two-phase structure: Pt nanoparticle-modified IrCu alloy. The Pt–IrCu/C catalyst was found to have not only a large electrochemically active specific area (S _EAS) but also good CO oxidation ability for oxidation of ethanol compared to the commercial Pt/C electrocatalyst using cyclic voltammetry. Furthermore, the Pt current density of Pt–IrCu/C was more than 1.6 times as high as that of Pt/C for ethanol oxidation. The Pt–IrCu/C catalyst also exhibited more efficient usage of Pt and enhanced the stability of ethanol electro-oxidation compared with a Pt/C catalyst.     

Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation

To maximize the utilization of catalysts and thereby reduce the high price, a new strategy was developed to prepare highly dispersed Pt-SnO_x nanoparticles supported on 8-Hydroxyquinoline (HQ) functionalized multi-walled carbon nanotubes (MWCNTs). HQ functionalized MWCNTs (HQ-MWCNTs) provide an ideal support for improving the utilization of platinum-based catalysts, and the introduction of SnO_x to the catalyst prevents the CO poisoning effectively. The as-prepared catalysts are characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It is found that the HQ functionalization process preserves the integrity and electronic structure of MWCNTs, and the resulting Pt-SnO_x particles are well dispersed on the HQ-MWCNTs with an average diameter of ca. 2.2 nm. Based on the electrochemical properties characterized by cyclic voltammetry and chronoamperometry, the Pt-SnO_x/HQ-MWCNTs catalyst displays better electrocatalytic activity and stability for the methanol oxidation. It is worth mentioning that the forward peak current density of Pt-SnO_x/HQ-MWCNTs catalyst is ca. 1.9 times of that of JM commercial 20% Pt/C catalyst, which makes it the preferable catalyst for direct methanol fuel cells.     

Influence of NH<Subscript>3</Subscript> flow rate on pyridine-like N content and NO electrocatalytic oxidation of N-doped multiwalled carbon nanotubes

Nitrogen-doped multiwalled carbon nanotubes (N-MWCNTs) have been prepared by pyrolysis of pyridine and iron phthalocyanine over an iron catalyst at 850 °C at various ammonia gas (NH₃) flow rates. X-ray photoelectron spectroscopy results reveal that the pyridine-like nitrogen (N) content can be controlled by changing the flow rate of NH₃, and that pyridine-like N plays an important role: it can increase the electrocatalytic activity and the rate of nitric oxide (NO) electrooxidation and decrease the activation energy of NO electrooxidation. Cyclic voltammetry results demonstrate that the N-MWCNTs sample grown with 200 mL/min NH₃ flow has the maximum N content of 3.22 atomic %, and its content of pyridine-like N that is chemically active is also the highest among all the N-MWCNTs samples. Electrochemical impedance spectroscopy results indicate that two-step electron transfer process occurs at the N-MWCNT-modified electrode, and the control step is different in various potential regions. The stability of NO electrooxidation at the N-MWCNT-modified electrode is examined, and the reaction mechanism is discussed.     

Electrochemical deposition of Bi2Te3-based thin films

The electrochemical reduction processes on stainless-steel substrates from an aqueous electrolyte composed of nitric acid, Bi³⁺, HTeO₂⁺, SbO⁺ and H₂SeO₃ systems were investigated using cyclic voltammetry. The thin films with a stoichiometry of Bi₂Te₃, Bi_0.5Sb_1.5Te₃ and Bi₂Te_2.7Se_0.3 have been prepared by electrochemical deposition at selected potentials. The structure, composition, and morphology of the films were studied by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM) and electron microprobe analysis (EMPA). The results showed that the films were single phase with the rhombohedral Bi₂Te₃ structure. The morphology and growth orientation of the films were dependent on the deposition potentials.     

Electrochemical performance of CeO<Subscript>2</Subscript> nanoparticle-decorated graphene oxide as an electrode material for supercapacitor

Cerium oxide nanoparticles and cerium oxide nanoparticle-decorated graphene oxide (GO) are synthesized via a facile chemical coprecipitation method in the presence of hexadecyltrimethylammonium bromide (CTAB). Nanostructure studies and electrochemical performances of the as-prepared samples were systematically investigated. The crystalline structure and morphology of the nanocomposites were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transition electron microscopy (TEM), Raman spectrum, and X-ray photoelectron spectroscopy (XPS). Electrochemical properties of the CeO₂ electrode, the GO electrode, and the nanocomposites electrodes were investigated by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS) measurements. The CeO₂ nanoparticle-decorated GO (at the mole ratio of CeO₂/GO = 1:4) electrode exhibited excellent supercapacitive behavior with a high specific capacitance of 382.94 F/g at the current density of 3.0 A/g. These superior electrochemical features demonstrate that the CeO₂ nanoparticle-decorated GO is a promising material for next-generation supercapacitor systems.