Facile synthesis of ZnTe/Quinhydrone nanocomposite as a promising catalyst for electro-oxidation of ethanol in alkaline medium

In this work, we introduce a novel ZnTe/quinhydrone (ZnTe/QH) nanocomposite as an excellent catalyst for electro-oxidation of ethanol in alkaline medium. The ZnTe semiconductor nanorods were synthesized by a novel chemical route. The synthesized product was characterized by field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), FT-IR spectroscopy, and cyclic voltammetry techniques. Then, this product along with quinhydrone were used for the electrocatalytic oxidation of ethanol in alkaline medium. The ZnTe/QH/GCE showed a higher electrocatalytic activity toward ethanol oxidation. The performance of catalyst was evaluated by electrochemical measurements such as cyclic voltammetry and electrochemical impedance spectroscopy using the three-electrode system. Furthermore, the ZnTe/QH/GCE displayed a higher stability with 93% retention of the initial current density after 6000 s in long term current-time curve. This newly prepared ZnTe/QH nanohybrid could be a promising anodic catalyst for the direct ethanol fuel cells (DEFCs) application.     

Temperature dependence on methanol oxidation and product formation on Pt and Pd modified Pt electrodes in alkaline medium

The effect of temperature on the catalytic oxidation of methanol on electrodeposited platinum and platinum-palladium alloy were carried out for a temperature range of 293-353 K. The morphology of the catalyst surface was studied using scanning electron microscopy, where as the structure and bulk composition of the Pt-Pd/C catalyst were determined by X-ray diffraction and energy dispersive X-ray spectroscopy. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were used to investigate the electrochemical parameters related to electro-oxidation of methanol under the influence of temperature. Apparent activation energies of the oxidation reactions on Pt/C and Pt-Pd/C were determined at different potentials within the same temperature range. A pronounced influence of temperature towards methanol oxidation was observed on the Pt-Pd/C catalyst as compared to Pt alone. The incorporation of Pd into Pt decreases the charge transfer resistance and activation energy of the methanol oxidation substantially which ensures greater tolerance of this catalyst towards methanolic residues. Quantitative analysis of the oxidation reaction product by ion chromatography further substantiates the much better performance of the Pt-Pd electrode than Pt alone for electrocatalytic oxidation of methanol in alkaline medium.     

Electrochemical deposition of Au–Pt alloy particles with cauliflower-like microstructures for electrocatalytic methanol oxidation

Au–Pt alloy particles with cauliflower-like microstructures of varying Pt/Au ratios were electrodeposited on indium tin oxide (ITO) substrates by constant potential electrolysis at E = −0.25 V. The results of X-ray diffraction and X-ray photoelectron spectroscopy confirm that the bimetallic alloys can be obtained for different Pt/Au ratios including 4/1, 1/1 and 1/4. The formation of alloyed cauliflower-like microstructures may be the result of the fast formation of gold seeds as the core and subsequent simultaneous deposition of Au and Pt from cyclic voltammetric study. The effect of surface composition of Au–Pt alloy particles on electrocatalytic methanol oxidation were investigated in H₂SO₄ solution. The electrocatalytic abilities including electrochemical surface area, peak current density and the turnover number of methanol oxidation follow the order of Pt₄Au₁ > Pt > Pt₁Au₁. The results can be ascribed to that electronic effect may be prominent while bifunctional effect is insignificant for Au–Pt alloy systems because the electrocatalytic activity of Au is negligible in acidic media. Additionally, the Pt₄Au₁ electrode has superior kinetics of methanol electro-oxidation than monometallic Pt electrode by calculating the electron transfer coefficient (α).     

One-step synthesis in deep eutectic solvents of PtV alloy nanonetworks on carbon nanotubes with enhanced methanol electrooxidation performance

We report a simple one-step chemical reduction strategy in deep eutectic solvents (DESs) for the fabrication of a PtV alloy nanonetwork (ANN)/multiwalled carbon nanotube (MWCNT) nanohybrid, which exhibits excellent electrocatalytic performance in both activity and stability for the methanol oxidation reaction (MOR). The as-synthesized nanohybrid was characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy, confirming the formation of a porous nanonetwork structure composed of smaller PtV alloy nanoparticles (~3.8 nm) and the presence of strong electronic transfer interactions between Pt and alloyed V. The electrochemical properties of catalysts for the MOR were evaluated by using cyclic voltammetry and chronoamperometry techniques. The electrocatalytic activity, durability and CO tolerance ability of PtV ANNs/MWCNTs toward the MOR are found to be considerably higher than those of the Pt/MWCNT and commercial Pt/C catalysts. This investigation of the effect of several reaction parameters (e.g., scan rate and methanol concentration) indicates that the electrocatalytic oxidation of methanol on PtV ANNs/MWCNTs is a diffusion-controlled electrochemical process. The performance enhancement mechanism of MOR on the PtV ANN/MWCNT catalyst is analyzed based on the structure and electrochemical studies.     

Preparation of PtNi hollow nanospheres for the electrocatalytic oxidation of methanol

We report the synthesis and characterization of hollow PtNi nanospheres by chemical successive-reduction method. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) account for the alloy formation between Pt and Ni and electronic structure change of Pt in the alloy. The prepared nanospheres show a high activity and stability for electrocatalytic oxidation of methanol as compared to the commercial Pt/C catalyst and the co-reduced PtNi nanoparticles. The reasons of the high electrocatalytic activity of the hollow PtNi nanospheres were discussed.     

Hierarchical reduced graphene oxide supported dealloyed platinum–copper nanoparticles for highly efficient methanol electrooxidation

Exploiting highly efficient electrocatalysts through simple methods is very critical to the development of energy conversion technologies. Herein, we develop a hierarchical reduced graphene oxide supported dealloyed platinum–copper nanoparticle catalyst (Pt–Cu/RGO) by a facile one-step electrodeposition of graphene oxide in the presence of H₂PtCl₆ and copper ethylenediamine tetraacetate. The nanostructure and composition were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Meanwhile, the electrocatalytic performance was investigated by cyclic voltammetry and chronoamperometry, showing that the Pt–Cu/RGO catalyst not only equips with an outstanding electrocatalytic activity for the methanol oxidation reaction (2.3 times that of commercial Pt/C catalyst), but also shows a robust durability and superior tolerance to CO poisoning. The excellent electrocatalytic performance could be attributed to the three-dimensional hierarchical structure, porous dealloyed nanoparticles and synergistic effect between each component.     

Electrodeposition of Pt–Ru and Pt–Ru–Ni nanoclusters on multi-walled carbon nanotubes for direct methanol fuel cell

A full-electrochemical method is developed to deposit three dimension structure (3D) flowerlike platinum-ruthenium (PtRu) and platinum-ruthenium-nickel (PtRuNi) alloy nanoparticle clusters on multi-walled carbon nanotubes (MWCNTs) through a three-step process. The structure and elemental composition of the PtRu/MWCNTs and PtRuNi/MWCNTs catalysts are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray polycrystalline diffraction (XRD), IRIS advantage inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The presence of Pt(0), Ru(0), Ni(0), Ni(OH)₂, NiOOH, RuO₂ and NiO is deduced from XPS data. Electrocatalytic properties of the resulting PtRu/MWCNTs and PtRuNi/MWCNTs nanocomposites for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) are investigated. Compared with the Pt/MWCNTs, PtNi/MWCNTs and PtRu/MWCNTs electrodes, an enhanced electrocatalytic activity and an appreciably improved resistance to CO poisoning are observed for the PtRuNi/MWCNTs electrode, which are attributed to the synergetic effect of bifunctional catalysis, three dimension structure, and oxygen functional groups which generated after electrochemical activation treatment on MWCNTs surface. The effect of electrodeposition conditions for the metal complexes on the composition and performance of the alloy nanoparticle clusters is also investigated. The optimized ratios for PtRu and PtRuNi alloy nanoparticle clusters are 8:2 and 8:1:1, respectively, in this experiment condition. The PtRuNi catalyst thus prepared exhibits excellent performance in the direct methanol fuel cells (DMFCs). The enhanced activity of the catalyst is surely throwing some light on the research and development of effective DMFCs catalysts.     

Facile synthesis of binary NiCoS nanorods supported on nickel foam as efficient electrocatalysts for oxygen evolution reaction

A facile two-step method has been applied to synthesize novel binary metal NiCoS nanorods supported on nickel foam (NF) as electrocatalysts for oxygen evolution reaction (OER). Firstly, electrodeposition process is conducted to fabricate binary Ni-Co hydroxides on NF (NiCo/NF). Then, a hydrothermal sulfuration of NiCo/NF has been adopted to prepare NiCoS nanorods arrays uniformly grown on the surface of NF (NiCoS/NF). XRD indicates that NiCoS/NF has mixed crystal phases of Ni₃S₂, CoS and Co₉S₈. SEM images display the uniform NiCoS nanorods composed of many vertical nanosheets on the surface, implying more exposed active sites. OER measurements demonstrate that NiCoS/NF has better activity with an overpotential of 370 mV to reach 100 mA cm^?2 than NiCo/NF and CoS_x/NF. Electrochemical impedance spectroscopy (EIS) tests confirm the faster charge-transfer rate of NiCoS/NF and smaller Tafel slope derived from binary NiCoS, implying the excellent electrocatalytic performances of binary metal sulfides.     

Fabrication of a bimetallic Cu/Pt particle-modified carbon nanotube paste electrode and its use for the electrocatalytic oxidation of methanol

In this work, carbon nanotube paste electrode (CNTPE) was used as a substrate for deposition of bimetallic Cu/Pt particles. At first, a Cu film was prepared by electrochemical reduction of Cu ions onto the CNTPE in 0.1 M H₂SO₄ solution. Cu/Pt catalysts were prepared by partial galvanic replacement of Cu with Pt by simply immersion of the Cu-coated CNTPE in 2.0 mM H₂PtCl₆ solution. The nature and surface morphology of the bare CNTPE and fabricated Cu/Pt species were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. The Cu/Pt-modified CNTPE exhibits remarkable electrocatalytic activity towards methanol oxidation. It has been shown that carbon nanotubes improve the electrocatalytic activity of the catalysts towards oxidation. Then, the influence of various parameters such as Cu source concentration, electrodeposition time, replacement time, and methanol concentration on its oxidation as well as long-term stability of the modified electrode have been investigated by electrochemical methods.     

Facile fabrication and electrocatalytic activity of Pt0.9Pd0.1 alloy film catalysts

A nano-thickness porous Pt_0.9Pd_0.1 alloy film with a greatly enhanced surface area were firstly synthesized at a glassy carbon electrode (GCE) using a facile cyclic voltammetry (CV) method. The atomic ratio of the alloy can be controlled by controlling the composition of the electrodeposition solution. We found that small amount of alloying Pd is an excellent catalytically enhancing agent for the Pt catalyst, and 10% Pd is the optimal. The structures of the Pt_0.9Pd_0.1 alloy film were characterized by FE-SEM, XPS, XRD and electrochemical techniques. It was found that the Pt_0.9Pd_0.1 film was in nanoporous structure and consisted of crystallites of 10.1 nm on average, leading to the modified electrode (Pt_0.9Pd_0.1/GCE) has an effective surface area as large as 790 times that of a corresponding bare Pt disk electrode. The Pt_0.9Pd_0.1/GCE exhibited significantly higher stability and catalytic activity for both of the methanol electro-oxidation reaction (MOR) and the oxygen electro-reduction reaction (ORR) than the correspondingly electrodeposited Pt modified GCE. The advantage can be attributed to the CV-prepared nano-porous structure on the electrode surface. This method and the prepared electrode can be expected to have promising applications in biosensors and fuel cells, etc.     

Pt support of multidimensional active sites and radial channels formed by SnO2 flower-like crystals for methanol and ethanol oxidation

SnO₂ nanoflowers and nanorods have been synthesized by the hydrothermal method without using any capping agent. Both types of SnO₂ nanostructures are selected as a support of Pt catalyst for methanol and ethanol electrooxidation. The synthesized SnO₂ nanostructures and SnO₂ supported platinum (Pt/SnO₂) catalysts are characterized by X-ray diffraction, scanning electron microscope and high resolution transmission electron microscope. The electrocatalytic properties of the Pt/SnO₂ and Pt/C catalysts for methanol and ethanol oxidation have been investigated systematically by typical electrochemical methods. The influence of SnO₂ morphology on its electrocatalytic activity is comparatively investigated. The Pt/SnO₂ flower-shaped catalyst shows higher electrocatalytic activity and better long-term cycle stability compared with other electrocatalysts owing to the multidimensional active sites and radial channels of liquid diffusion.     

Catalytic activity of platinum/tungsten oxide nanorod electrodes towards electro-oxidation of methanol

Tungsten oxide (WO₃) nanorods are synthesized using an Anodisc alumina membrane as a template and platinum nanoparticles are supported on the nanorods. The nanorods, serving as platinum catalyst supports, are characterized by electron microscopy and by electrochemical analysis. Methanol oxidation on the prepared electrodes is studied by means of cyclic voltammetry and chronopotentiometry. A film of Pt/WO₃ nanorods on a glassy carbon electrode exhibits good electrocatalytic activity towards the oxidation of methanol. High electrocatalytic activities and good stabilities are attributed to a synergistic effect between Pt and WO₃ that avoids poisoning of the electrodes.     

The formation of wrapping type Pt–Ni alloy on three-dimensional carbon nanosheet for electrocatalytic oxidation of methanol

In this paper, the PtNi alloy was embedded into the surface layer of three-dimensional carbon nanosheets (CNSs) with a special layered structure. We controllably adjusted the ratio of Pt/Ni to form large particle alloy with Pt coating Ni and a small number of hollow PtNi alloy pellets. The electro-catalytic methanol oxidation activity and durability of the catalysts were estimated by cyclic voltammetry and chronoamperometric techniques. The results indicated that the doping of Ni effectively improved the activity and anti-poisoning of the catalyst in the methanol electrocatalytic oxidation reaction (MOR). Transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption techniques, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to explore the composition, morphology and structure of these catalysts. It is discovered that the Pt–Ni/CNSs (2:1) sample exhibits the best MOR activity with a peak current density of 15.03 mA cm^?2 at the forward scan due to the excellent lamellar structure, good crystallinity and abundant pore structure of CNSs, which is benefit to form ultrahigh specific surface area, superb electron and ionic conductivity.     

Macroporous Pt modified glassy carbon electrode: Preparation and electrocatalytic activity for methanol oxidation

Three-dimensional (3D) macroporous Pt (MPPt) with highly open porous walls has been successfully synthesized using the hydrogen bubble dynamic template synthesis and galvanic replacement reaction. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods were adopted to characterize their structures and properties. The resulting MPPt shows the same morphology as the initial 3D copper. The MPPt modified glassy carbon electrode (MPPt/GCE) exhibits excellent catalytic activity toward methanol oxidation. The present strategy is expected to reduce the cost of the Pt catalyst remarkably.     

Hydrogen evolution assisted electrodeposition of bimetallic 3D nano/micro-porous PtPd films and their electrocatalytic performance

Self-supporting PtPd bimetallic catalysts with three-dimensional (3D) porous structures and a greatly enhanced surface area are firstly fabricated at a glassy carbon electrode (GCE) by a one-step strategy of potentiostatic co-electrodeposition utilizing hydrogen bubble dynamic templates. The atomic ratio of Pt/Pd in the bimetallic catalysts is varied by changing the composition of the electrodeposition solution. The 3D porous PtPd films are characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) and examined as electrocatalysts for the electro-oxidation of methanol using cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). Experimental results demonstrate that a small amount of Pd plays the predominant role in the formation of 3D porous structure for PtPd bimetallic catalysts and is an excellent catalytically enhancing agent for the Pt catalyst towards methanol electro-oxidation. The study on electrocatalytic performance of mono and bimetallic catalysts towards formic acid electro-oxidation also reveals the better activity of 3D porous Pd film for this reaction.     

Platinum–Iron nanoparticles supported on reduced graphene oxide as an improved catalyst for methanol electro oxidation

Platinum–Iron nanoparticles supported on reduced graphene oxide powder are synthesized by chemical reduction method as an anode catalyst for the methanol electro oxidation. The characterization of the catalyst has been investigated using physical and electrochemical methods. Prepared catalyst was characterized by scanning electron microscopy (SEM), TEM (Transmission electron microscopy), FT-IR (Fourier-transform infrared spectroscopy), Raman spectroscopy and, X-ray diffraction (XRD) and energy dispersive analysis of X-ray (EDX). Pt and Pt-Fe nanoparticles are uniformly dispersed on the surface of reduced graphene oxide (rGO) powder nanocomposite support. The catalytic properties of the catalyst for methanol electro-oxidation were thoroughly studied by electrochemical methods that involved in the cyclic voltammetry, linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The Pt-Fe/rGo exhibits high electrocatalytic activity, catalyst tolerance for the CO poisoning and catalyst durability for electro-oxidation of methanol compared to the Pt/rGo and commercial Pt/C catalyst. Therefore, the Pt-Fe/rGo catalyst is a good choice for application in direct methanol fuel cells.     

Excellent dispersion and electrocatalytic properties of Pt nanoparticles supported on novel porous anatase TiO2 nanorods

We synthesize, for the first time, a new Pt based catalyst for direct methanol fuel cells using homemade novel porous anatase TiO₂ nanorods as a new catalyst support. Pt nanoparticles are prepared by an improved ethylene glycol reduction method and supported on the surface of TiO₂ with excellent dispersion and without any aggregates. The structure and elemental composition of the TiO₂ and Pt/TiO₂ catalyst are characterized by transmission electron micrography (TEM), nitrogen sorption, energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The electrocatalytic properties of the Pt/TiO₂ catalyst for methanol and carbon monoxide electro-oxidation reactions are investigated by cyclic voltammetry (CV) in an acidic medium. Apparent electrocatalytic activity for methanol electro-oxidation reaction, high carbon monoxide tolerance and good stability are all observed for the Pt/TiO₂ catalyst. These may be attributed to the excellent dispersion of the Pt nanoparticles and the special properties of the TiO₂ support. These results imply that this Pt/TiO₂ catalyst has promising potential applications in direct methanol fuel cells.     

Pt modified TiO2 nanotubes electrode: Preparation and electrocatalytic application for methanol oxidation

Pt nanoparticles decorated TiO₂ nanotubes (Pt/TiO₂NTs) modified electrode has been successfully synthesized by depositing Pt in TiO₂NTs, which were prepared by anodization of the Ti foil. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods were adopted to characterize their structures and properties. The Pt/TiO₂NTs electrode shows excellent electrocatalytic activity toward methanol oxidation reaction (MOR) in alkaline electrolyte without UV irradiation.     

Pt–Ru nanoparticles anchored on poly(brilliant cresyl blue) as a new polymeric support: Application as an efficient electrocatalyst in methanol oxidation reaction

The glassy carbon electrode is modified by poly(brilliant cresyl blue) (PBCB) to be applied as a new green and efficient platform for Pt and Pt–Ru alloy nanoparticles deposition. Surface composition, morphology and catalytic activity of these modified electrodes towards methanol oxidation are assessed by applying X-ray diffraction, field emission scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The X-ray diffraction patterns reveal that the highly crystalline Pt and Pt–Ru alloy and RuO₂ nanoparticles with low crystallinity are deposited on the PBCB modified glassy carbon electrodes. The microscopic images indicate smaller size and better distribution of deposited nanoparticles on the surface of PBCB modified electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy results reveal that PBCB supported Pt and Pt–Ru nanoparticles have better electrocatalytic performance and durability towards methanol oxidation rather than the unsupported nanoparticles. From the obtained results it can be concluded that the presence of PBCB not only improves the stability of nanoparticles on the surface, but also leads to the formation of smaller size and more uniform distribution of nanoparticles on the surface, which, in turn, cause the nanoparticles to provide a higher accessible surface area and more active centers for the oxidation of methanol. The results will be valuable in extending the applications of this polymer in surface modification steps and in developing promising catalyst supports to be applied in direct methanol fuel cells.     

Bimetallic AuPt alloy nanodendrites/reduced graphene oxide: One-pot ionic liquid-assisted synthesis and excellent electrocatalysis towards hydrogen evolution and methanol oxidation reactions

Herein, reduced graphene oxide supported well-dispersed bimetallic AuPt alloy nanodendrites (AuPt ANDs/rGO) were fabricated by a one-pot coreduction approach using ionic liquid (1-aminopropyl-3-methylimidazolium bromide, [APMIm]Br) as the stabilizer and capping agent. There is no any other polymer or seed involved. Characterized measurements include transmission electron microscopy (TEM), high angle annular dark-field scanning TEM (HAADF-STEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The typical samples displayed excellent electrocatalytic activity and durability towards hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR) in contrast with Pt nanocrystals/rGO and commercial Pt/C (50%) catalysts, which make it promising for practical catalysis in energy conversion and storage.