A novel co-electrodeposited Co/MoSe2/reduced graphene oxide nanocomposite as electrocatalyst for hydrogen evolution

In this study, a simple and fast electrochemical method was employed to synthesis molybdenum diselenide thin film. The morphology, structure and chemical composition of the nanocomposites were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The progressive effects of transition metal ions including Ni, Cu, and Co were surveyed on the hydrogen evolution activity of MoSe₂ thin films. Co/MoSe₂ nanocomposite thin films has significant electrocatalytic activity as compared to other samples, In order to achieve higher performance, preparing Co/MoSe₂/RGO nanocomposite thin film, two strategies including layer by layer electrodeposition and co-electrodeposition has been employed. The presence of reduced graphene oxide leading to the onset potential shifts to more positive values and increase the current density. Also, results showed that the Co/MoSe₂/RGO nanocomposite prepared by co-electrodeposition exhibits the best electrochemical hydrogen evolution at onset potential of −0.18 with an overpotential of −0.45 V.     

A UPD-spontaneous redox approach to the preparation of monolayer palladium on reduced graphene oxide-supported gold nanoparticles for ethanol electrooxidation in alkaline media

Monolayer Pd on electrochemical-reduced graphene oxide supported Au nanoparticles (m-Pd–Au/ERG) was designed by a simple and effective route, which produces electrocatalyst with a considerably low Pd loading and good electrocatalytic performance for ethanol oxidation. The as-prepared m-Pd–Au/ERG nanocompostie was characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results show that high-density m-Pd–Au nanoparticles are dispersed on the surface of ERG uniformly. The electrochemical activities of the as-prepared nanocomposites toward ethanol oxidation in alkaline media were investigated by using cyclic voltammetry and chronoamperometric technique. The results demonstrate that the m-Pd–Au/ERG catalyst shows much higher electrocatalytic activity, stronger tolerance to CO than the m-Pd–Au and b-Pd–Au/ERG catalysts for ethanol oxidation.     

Reduced graphene oxide-supported nickel oxide catalyst with improved CO tolerance for formic acid electrooxidation

The superior catalytic activity along with improved CO tolerance for formic acid electrooxidation has been demonstrated on a NiO-decorated reduced graphene oxide (rGO) catalyst. The cyclic voltammetry response of rGO–NiO/Pt catalyst elucidates improved CO tolerance and follows direct oxidation pathway. It is probably due to the bene?cial effect of residual oxygen groups on rGO support which is supported by FT-IR spectrum. A strong interaction of rGO support with NiO nanoparticles facilitates the removal of CO from the catalyst surface. The chronoamperometric response indicates a higher catalytic activity and stability of rGO–NiO/Pt catalyst than the NiO/Pt and unmodified Pt electrode catalyst for a prolonged time of continuous oxidation of formic acid.     

Comparison of ethanol electro-oxidation on Pt/C and Pd/C catalysts in alkaline media

The ethanol electro-oxidation behaviors of Pt/C and Pd/C in alkaline media were compared using potentiodynamic and potentiostatic methods. Various ethanol and alkaline concentrations were studied. In addition, the temperature effect of ethanol oxidation was investigated. The Pd/C showed a higher activity toward ethanol oxidation than the Pt/C, especially in the potentiostatic measurement. This is mainly due to the higher oxyphilic characteristics of the Pd/C and the relatively inert nature of the Pd/C on C–C bond cleavage. The apparent activation energies of the ethanol oxidation on the Pd/C in alkaline media varied from 26.6 to 30.4 kJ mol⁻¹, depending on the potentials. The Tafel slopes could be divided into two parts on both catalysts: at low overpotentials, the Tafel slope on both the Pt/C and the Pd/C was close to 120 mV dec⁻¹ at all temperatures; at high overpotentials, the Tafel slope was ca. 260 mV dec⁻¹ on the Pd/C at all temperatures, but was much higher on the Pt/C, especially at high temperatures. Based on these results, it is concluded that Pd/C has less poisoning effect and higher activity than Pt/C for selective oxidation of ethanol to acetate.     

Preparation and electrocatalytic characteristics of the Pt-based anode catalysts for ethanol oxidation in acid and alkaline media

The current study reports the preparation and investigation of several Pt-based anode catalysts loaded on reduced graphene oxide (rGO) as electrocatalysts in both acid and alkaline media for ethanol electrooxidation. The synthesized catalysts are evaluated by the method of XRD, Raman spectroscopy, XPS and TEM. Electrocatalytic properties of these catalysts for ethanol oxidation were investigated by cyclic voltammetry and chronoamperometry. It was found that the as-prepared nanocatalysts doped by metals and oxide metals showed the improvement of catalytic performance compared to Pt-only supported on graphene catalyst. The results indicated that the presence of Al favoured Pt nanoparticles dispersing on the surface of rGO sheets. Indeed, the PAG catalyst exhibits the highest mass activity for the ethanol oxidation of 1194 mA mg^?1_Pt in acid medium and 3691 mA mg^?1_Pt in alkaline medium. In addition, the PAG catalyst also shows good antipoisoning ability for ethanol electrooxidation in both media. This catalyst could be a potential catalyst for direct ethanol fuel cell (DEFC).     

Electrochemical layer-by-layer fabrication of a novel three-dimensional Pt/graphene/carbon fiber electrode and its improved catalytic performance for methanol electrooxidation in alkaline medium

Here, we report a novel method for assembling reduced graphene oxide (RGO) and Pt nanoparticles on a carbon fiber (CF) electrode successively to form a stable Pt nanoparticle-RGO-Pt nanoparticle-RGO/CF multiple junction for electrocatalysis application. As the SEM imaging exhibited, Pt nanoparticles are uniformly deposited on the surface of each RGO sheet, performing an alternative covering structure of RGO and Pt nanoparticle multi-layer on the CF electrode. Thus, a novel three-dimensional (3D) multi-layered Pt/RGO modified CF electrode (N–Pt/RGO/CF) is obtained. Experimental results demonstrate that the prepared N–Pt/RGO/CF electrode shows good electrochemical properties and enhanced electrocatalytic activity toward methanol electrooxidation in alkaline medium as compared with the Pt/RGO/CF electrode without layer-by-layer structure or the Pt/CF electrode without RGO. It is due to the unique 3D pore structure of N–Pt/RGO/CF and the good electron transport property of RGO in the composite electrode.     

Co(OH)2 nanoparticles deposited on reduced graphene oxide nanoflake as a suitable electrode material for supercapacitor and oxygen evolution reaction in alkaline media

In this work, cobalt hydroxide nanoparticles are simply synthesized (size is about 50 nm) and deposited on the reduced graphene oxide nanoflake by the hydrothermal method. Then, the ability of glassy carbon electrode modified with this low-cost nanocomposite is examined as a supercapacitor and oxygen evolution electrocatalysts in 2.0 mol L^?1 KOH by a three-electrode system. The modified electrode as a pseudocapacitor with potential windows of 0.35 V, exhibits a powerful specific capacitance (235.20 F g^?1 at 0.1 A g^?1 current density), energy density, stability (about 90% of the initial capacitance value maintain after 2000 cycles at 1.0 A g^?1) and fast charge/discharge ability. Furthermore, the modified electrode displays a good electrocatalytic activity for oxygen evolution reaction with a current density of 10.0 mA cm^?2 at 1.647 V, small Tafel slope of 56.5 mV dec^?1, good onset potential of 1.521 V vs. RHE and suitable durability.     

Three dimension (3D) hierarchical electrode (Au/rGO/CoPt3) for electrooxidation of ethanol in fuel cells

A highly efficient electrode for ethanol electrooxidation was successfully fabricated with the assistance of Nanoimprint Lithography (creation of 3D structure) and facile preparation method-electrodeposition. Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), X-ray Diffraction (XRD) and Raman spectroscopy were used to characterize the electrodes obtained, which were further evaluated by Cyclic Voltammetry Potentiostat. It concludes that the electrocatalytic activity of the electrodes towards ethanol oxidation is promoted in the sequence of Au < Au/rGO < Au/rGO/CoPt₃. The synergy effect of reduced GO and CoPt3 nanoparticle along with highly active gold thin layer forming 3D structure is responsible for the significant improvement of the catalysis.     

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.     

Facile scalable manufacture of improved electrodes using structured surface coatings of nickel oxide as cathode and reduced graphene oxide as anode for evaluation in a prototype development on microbial fuel cells

Improvement of the microbial fuel cell performance is highly required in energy production associated with domestic sewage treatment. For this objective, metal electrodes coated with specific materials for anode and cathode were manufactured. Materials such as reduced graphene oxide (rGO) as an anode, with high electrical conductivity, and structured nickel oxide (sNiO), which act as air cathode, could be the key to obtaining substantial improvements in the production of energy and treatment of domestic sewage. In this work, simple methods were developed to coat the stainless steel meshes with rGO and sNiO, used in MFC prototypes. The results show that the methodologies developed for the coating of the electrodes aid to improve the performance of the MFC in the delivery of potential, current density and power density up to 220%, 140% and 700% respectively, compared to the blank stainless steel electrodes; while the COD levels in the water purified by the MFC with covered electrodes reached a decrease of 36% compared to the same system without covered electrodes. Additionally, the built MFCs prototypes were tested as a power supply for a digital clock and an LED light.     

Platinum-palladium nanoparticles-loaded on N-doped graphene oxide/polypyrrole framework as a high performance electrode in ethanol oxidation reaction

Existing catalysts for ethanol oxidation in direct ethanol fuel cells (DEFC) are faced to significant challenges due to their poor performance and CO like intermediates poisoning tolerance at anode surface. Hence researchers are looking for new electrocatalysts in the ethanol oxidation. In this study, polypyrrole/N-doped graphene oxide (PPy/NGO) nanocomposite was prepared using in-situ polymerization method. Next the platinum-palladium (PtPd) was electrochemically decorated on PPy/NGO nanocomposite surface. In order to ensure the correct preparation of nanocomposite, fourier transform infrared spectroscopy (FT-IR) analysis was carried out to peruse the chemical structure of the nanocomposite and also to investigate their morphology, field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) were used. The morphology of nanocomposite shows that PPy has penetrated into the space between NGO plates. Disparate electrochemical techniques like cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) were employed to evaluate the oxidation of ethanol. Results showed that PtPd/PPy/NGO exhibits improved electrocatalytic activity and stability for ethanol oxidation. Enhanced active surface area of the PtPd/PPy/NGO electrode (35.1 m² g^?1) contributes to increase in current density and decrease in over potential values in the ethanol oxidation as compared to PtPd electrocatalyst.     

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.     

Highly active iron (II) oxide-zinc oxide nanocomposite synthesized Thymus vulgaris plant as bioreduction catalyst: Characterization,hydrogen evolution and photocatalytic degradation

This study aimed to synthesize an iron (II) oxide-zinc oxide (Fe₂O₃/ZnO) nanocomposite using eco-friendly methods and to evaluate its performance as a catalyst against textile dyes and hydrogen generation. To these means, Fe₂O₃/ZnO was synthesized from the Thymus vulgaris plant by biogenic methods. The resulting nanocomposite was characterized by Fourier Transmission Infrared Spectroscopy, Transmission Electron Microscopy (TEM), UV–vis spectrometry, and X-Ray diffraction patterns (XRD). According to the obtained TEM characterization results, it was observed that the nanocomposite had an average size of 3.78 nm. According to the XRD results, the nanocomposite's average crystal size was 3.884 nm. In addition, the hydrogen release was investigated by NaBH₄ hydrolysis. The turnover frequency, activation energy (Ea), entropy (ΔS), and enthalpy (ΔH) values obtained from hydrogen production studies are 1942.23 h⁻¹ and 15.68 kJ/mol, −127.29 J/mol K, and 13.14 kJ/mol, respectively. In the reusability tests, it was observed that the nanocomposite was 78% effective. The photocatalytic studies using solar energy revealed that the nanocomposite was 79% effective for methylene blue (MB) dye removal. This work demonstrated the potential of transition metals for energy production. It showed that the developed nanocomposite could be a viable solution and, with further development, can be an efficient catalyst for alternative energy production (energy generation) and textile industry wastewater treatment.     

Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion-exchange membranes for alkaline fuel cells: Effect of silica content and the single cell performance

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid alkaline membranes with enhanced hydroxyl (OH⁻) conductivity are prepared in response to the relatively low conductivity of previously reported PPO-based systems. The membranes also exhibit higher swelling-resistant properties and the hydroxyl (OH⁻) conductivity values are comparable to previously reported fluoropolymer-containing membranes: 0.012-0.035 S cm⁻¹ in the temperature range 30-90 °C. Other favorable properties for fuel cell application include high tensile strengths up to 25 MPa and large ion-exchange capacities in the range 2.01-2.27 mmol g⁻¹. Beginning-of-life fuel cell testing of a membrane with a thickness of 140 μm yielded an acceptable H₂/O₂ peak power density of 32 mW cm⁻² when incorporated into an alkaline membrane electrode assembly. Therefore, this class of hybrid membrane is suitable for application in alkaline membrane fuel cells.     

Pd/Cu bimetallic nanoparticles supported on graphene nanosheets: Facile synthesis and application as novel electrocatalyst for ethanol oxidation in alkaline media

Well distributed Pd/Cu bimetallic nanoparticles supported on graphene nanosheets as novel electrocatalyst has been prepared via a facile synthetic method: started with an electroless deposition route to anchor Cu nanoseeds on graphene nanosheets, followed by a latter displacement reaction to achieve Pd/Cu overlaying nanostructure. The loading density and morphology of bimetallic nanoparticles on graphene are varied by adjusting the initial amount of Cu precursor and reducing agent proportionally. Scanning transmission electron microscopy (STEM) images combining energy dispersive X-ray spectroscopy (EDX) mapping results confirm the existance and distribution of Pd and Cu in the bimetallic nanoparticles, while transmission electron microscopy (TEM) reveals the nanoparticle size and overlaying nanostructure. Cyclic voltammograms tests for the hybrid electrocatalysts in 1.0 M KOH solution show a gradual increase of electrochemically active surface area (EASA) against the increment of nanoparticle loading. Meanwhile, a significantly enhanced tolerance to poisoning of electrocatalyst is observed by cyclic voltammograms curves for ethanol electrooxidation in alkaline media with high I_f/I_b ratios compared to previous research. The large enhancement on I_f/I_b ratios of the hybrid electrocatalysts can be ascribed to the well distributed overlaying bimetallic nanostructure supported on graphene nanosheets. The facilely prepared Pd/Cu/graphene hybrid materials demonstrate vastly superior electrocatalytic properties compared to the commercial Pd/C catalyst, indicating a great potential in fuel cells application.     

Preparation of Pt dendrites on Poly(diallyldimethylammonium chloride)-functionalized reduced graphene oxide as an enhanced electrocatalyst for the hydrogen evolution reaction in alkaline media

Herein, we describe the synthesis of Pt dendrites with electrochemically active high-index planes on poly(diallyldimethylammonium chloride)-functionalized reduced graphene oxide (PFG) using a newly developed high-voltage electrochemical reduction (HVER) method. Subsequently, the catalytic activities of the prepared samples for the hydrogen evolution reaction (HER) in 1 M NaOH are characterized. The HVER method facilitates the preparation of nanoparticles in short reaction times. This method allows Pt particles to be formed by electron transfer from the cathode to a Pt precursor. Importantly, Pt particles deposited on PFG (Pt/PFG), prepared by the addition of PVP, are revealed to comprise both two- (2D) and three-dimensional (3D) dendrite structures, featuring abundant step and edge sites. The various factors affecting the morphology and the ratio of 2D to 3D dendrites of Pt were determined by TEM analysis. The ratio of 2D to 3D Pt dendrites depends on the amount of PVP employed and has a direct influence on the electrochemically active surface area (ECSA) and HER activity. Namely, the prepared Pt/PFG sample with the highest density of 2D Pt dendrites exhibits the highest HER activity due to its high ECSA. The performance of Pt/PFG13 (prepared keeping the PVP:Pt ratio as 13:1) was compared with that of commercial 40 wt% Pt/C, and the Pt/PFG13 sample exhibited superior current density (−424 mA/cm_geo² for Pt/PFG13 and –242 mA/cm_geo² for commercial 40 wt% Pt/C at −1.5 V vs. Hg/HgO; approximately 1.8 times higher) and catalytic stability, implying that these parameters are positively correlated with the increased number of step and edge sites.     

AuNi alloy nanoparticles supported on reduced graphene oxide as highly efficient electrocatalysts for hydrogen evolution and oxygen reduction reactions

Bimetallic nanoparticles of Au and Ni in the form of alloy nanostructures with varying Ni content are synthesized on reduced graphene oxide (rGO) sheets via a simple solution chemistry route and tested as electrocatalysts towards the hydrogen evolution (HE) and oxygen reduction (OR) reactions using polarization and impedance studies. The AuNi alloy NPs/rGO nanocomposites display excellent electrocatalytic activity which is found to improve with increasing Ni content in the AuNi/rGO alloy nanocomposites. For HER, the best AuNi alloy NPs/rGO electrocatalyst, the one with the highest Ni content, exhibits high activity with an onset overpotential approaching zero versus the reversible hydrogen electrode and an overpotential of only 37 mV at 10 mA cm^?2. Additionally, a low Tafel slope of 33 mV dec^?1 and a high exchange current density of 0.6 mA cm^?2 are measured which are very close to those of commercial Pt/C catalyst. Also, in the ORR tests, this electrocatalyst displays comparable activity to Pt/C. The Koutecky–Levich plots referred to a 4-electron mechanism for the reduction of dissolved O₂ on the AuNi alloy NPs/rGO catalyst. The electrocatalyst thus demonstrates excellent activity towards HER and ORR. Additionally, it exhibits outstanding operational durability and activation after 10,000^th cycles assuring its practical applicability.     

Facile synthesis of Co3O4 nanoparticles from a novel tetranuclear cobalt(III) complex. Application as efficient electrocatalyst for oxygen evolution reaction in alkaline media

A tetranuclear cobalt complex [Co₄^III(L′)₆] was synthesized by the direct reaction of cobalt(II) acetate with a N₂S₂ Schiff base ligand H₂L containing a disulfide bond under aerobic conditions {H₂L = 2,2′-bis(2-hydroxynaphthyliminobenzyl)disulfide}. The X-ray crystal structure of [Co₄^III(L′)₆] indicates reductive disulfide bond scission of H₂L upon reaction with Co²⁺ to give [L^′]^2–. Furthermore, cobalt oxide nanoparticles of about 30 nm size were synthesized by thermal decomposition of [Co₄^III(L′)₆] as a precursor. The Co₃O₄ nanoparticles were characterized by XRD, FE-SEM, TEM, and FT-IR spectroscopy. The electrocatalytic activity of the resulting oxide was examined in oxygen evolution reaction (OER) by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) in 1.0 mol L^?1 KOH. The NPs displays efficient electrocatalytic activity for oxygen evolution reaction with a current density of 10.0 mA cm^?2 at 1.65 V, good onset potential of 1.52 V vs. RHE and small Tafel slope of 44 mV dec^?1.     

Enhanced electrocatalytic activity of nickel particles electrodeposited onto poly (m-toluidine) film prepared in presence of CTAB surfactant on carbon paste electrode for formaldehyde oxidation in alkaline medium

In this work, carbon paste electrode is coated with poly (m-toluidine) film by potentiodynamic electropolymerization of m-toluidine monomer in the presence of cetyltrimethyl ammonium bromide (CTAB-PMT/MCPE). Then electrolysis at fixed potential (−1.0 V versus reference electrode for 15 min) is employed for electrodepositing of Ni from 1.5 M NiSO₄ acidic solution at the surface of polymer-modified electrode for preparation of Ni/CTAB-PMT/MCPE. The general electrochemical behaviors of these modified electrodes are characterized by cyclic voltammetry in alkaline media. In alkaline medium (i.e. NaOH 0.1 M) a good redox behavior of Ni(III)/Ni(II) couple at the surface of these electrodes can be observed. The nickel particles electrodeposited at the surface of Ni/CTAB-PMT/MCPE exhibits a significant electrocatalytic activity towards oxidation of formaldehyde. Moreover, the effects of various parameters such as concentration of CTAB, concentration of formaldehyde, film thickness and monomer concentration on the electrooxidation of formaldehyde as well as long-term stability of the Ni/CTAB-PMT/MCPE have also been investigated.