Nickel nanorods over nickel foam as standalone anode for direct alkaline methanol and ethanol fuel cell

A highly electroactive nickel nanorod (NNR)/nickel foam (NF) electrode was fabricated for direct alcohol fuel cells (DAFCs) using a simple and cost-effective hydrothermal process. The Ni/NiO nanorods were successfully grown on the surface of an NF electrode, which strongly enhanced the anode wettability and increased surface area by 18 times (11.9 m² g⁻¹), resulting in interfacial polarization resistance reduction. The NNR/NF electrode shows high electro-catalytic activity and great stability during alcohol oxidation. The current densities obtained for NNR/NF were four (479 mA cm⁻²) and six (543 mA cm⁻²) times higher than that for pristine NF in the cases of methanol and ethanol oxidations, respectively. This high current density can be attributed to the superhydrophilic surface of the Ni/NiO nanorods and corresponding high mass transfer capability between the electrolytes and Ni/NiO nanorods embedded on the surface of the electrodes. This study presents a new approach for using the novel NNR/NF as a cheap and high performance anode in DAFCs.     

In situ electro-oxidation modulation of Ru(OH)x/Ag supported on nickel foam for efficient hydrogen evolution reaction in alkaline media

Transition metal hydroxides for hydrogen evolution reaction (HER) usually have been limited by poor intrinsic activity and weak conductivity. In our work, in situ electro-oxidation as an effective way has been used to modulate the electronic states of active sites for ruthenium hydroxides, which provides obviously enhanced activity for HER in alkaline media. Ag-modified nickel foam (NF) as substrate can provide the excellent conductivity to improve the charge transfer rate of Ru(OH)_x/Ag/NF. In situ electro-oxidation process has been conducted for Ru(OH)_x/Ag/NF through OER measurements in alkaline media, which results in the formation of more Ru (IV) as higher actives sites for HER. Compared to Ru(OH)_x/NF, X-ray photoelectron spectroscopy (XPS) and polarization curves prove that Ag doping in Ru(OH)_x/Ag/NF may contribute to the oxidization of ruthenium from Ru (III) to Ru (IV) during in situ electro-oxidation. The obtained Ru(OH)_x/Ag/NF exhibits Pt-like HER activity with a very low overpotential of 103.2 mV to drive 100 mA cm⁻² in 1.0 M KOH. The excellent stability of Ru(OH)_x/Ag/NF has also been demonstrated. Therefore, our work provides a new strategy by modulating valence state of active sites for transition metal hydroxides for efficient HER.     

Highly selective electrocatalytic hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran over AgCu nanoalloys

Electrochemical reactions are important method for reducing the carbon footprint of large-scale chemical processes. Highly selective conversion of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) is achieved under mild conditions through electrocatalytic hydrogenation (ECH) over AgCu nanoalloys supported by the pyrolyzed biomass alginic acid sodium (PA), with the advantage of utilizing the active hydrogen intermediates in the process. The Ag₁Cu₁/PA exhibits outstanding performance in ECH of HMF with a selectivity of 94% toward DHMF at a conversion of 93.2% and the Faraday efficiency (FE) of 61.8%, which are significantly superior to those over Ag/PA (selectivity of 53.89%, conversion of 90.6%, and FE 25.79%). The incorporation of Cu into Ag nanoparticles boosts the charge transferability and lowers the onset potential of ECH. Density functional theory calculations reveal that AgCu alloy provides more electron transfer to HMF and lowers the energy barrier for HMF hydrogenation.     

Enhanced alkaline/seawater hydrogen evolution reaction performance of NiSe2 by ruthenium and tungsten bimetal doping

The exploration of high-efficiency and stable electrocatalysts for alkaline and seawater hydrogen evolution reaction (HER) is the key to realize energy conversion, but there is still a significant challenge owing to the slow HER kinetics in alkaline and seawater systems. In this study, we prepared nickel foamed-supported Ru, W co-doped NiSe₂ (Ru, W–NiSe₂/NF) by a brief two-step hydrothermal strategy and the prepared Ru, W–NiSe₂/NF displays exceptional HER property, requiring only a low overpotential of 100 and 353 mV to reach 10 mA cm⁻² in 1 M KOH and natural seawater, respectively, far superior to Ru–NiSe₂/NF, W–NiSe₂/NF and NiSe₂/NF. Electrochemical surface area (ECSA) and operando electrochemical impedance spectroscopy (EIS) verify the abundant active sites and superior electron transfer rate of Ru, W–NiSe₂, which optimized the HER kinetics in alkaline solution and natural seawater. The ECSA normalization and TOF results indicated that Ru, W co-doping increased the intrinsic activity of NiSe₂. This study revealed the impact of bimetallic doping on the intrinsic activity of NiSe₂, and provided a practical strategy for designing and developing the HER electrocatalysts with excellent performance.     

Mixed-ceria reinforced acid functionalized graphene oxide-Nafion electrolyte membrane with enhanced proton conductivity and chemical durability for PEMFCs

Towards the next-gen energy solutions, Nafion, as a state-of-the-art polymer electrolyte to low temperature fuel cell (LTFC) application has been one of the most demanding hydrogen to clean energy conversion device ever achieved. However, the inherent issue of limiting chemical durability and restricted proton conductivity have always been a topic of concern with pure Nafion membranes. To tackle this, we report a mixed-ceria reinforced phosphorylated graphene oxide (sPGO)/Nafion membrane as a potential electrolyte to simultaneously improve the chemical durability and proton conductivity of bare Nafion by utilizing the redox property of ceria nanoparticles and acidic sites of sPGO for accelerated proton transfer. As a progressive method, the single-step phosphorylation of GO introduced short chain branching along with enhanced number of acidic sites in the Nafion matrix whereas incorporation of mixed-ceria nanoparticles improved the chemical durability of the membrane due to its superior radical scavenging property. As a result, mixed-ceria reinforced sPGO/Nafion (Ce-sPGO/NF) electrolyte membrane showed higher proton conductivity (1.2-times) and chemical durability (8.1-times) than bare Nafion. Furthermore, the polymer electrolyte membrane (PEM) was also showcased high enough thermomechanical and electrochemical stability at 80 °C and 100% relative humidity (RH).     

An asymmetric anthraquinone-modified carbon/ruthenium oxide supercapacitor

An asymmetric supercapacitor with improved energy and power density, relative to a symmetric Ru oxide device, has been constructed with anthraquinone-modified carbon fabric (Spectracarb 2225) as the negative electrode and Ru oxide as the positive electrode. The performance of the supercapacitor was characterized by cyclic voltammetry and constant current discharging. Use of the anthraquinone-modified electrode extends the negative potential limit that can be used, relative to Ru oxide, and allows higher cell voltages to be used. The maximum energy density obtained was 26.7 Wh kg⁻¹ and an energy density of 12.7 Wh kg⁻¹ was obtained at a 0.8 A cm⁻² discharge rate and average power density of 17.3 kW kg⁻¹. The C-AQ/Ru oxide supercapacitor requires 64% less Ru relative to a symmetric Ru oxide supercapacitor.     

The cleanup of CO in hydrogen for PEMFC applications using Pt,Ru, Co,and Fe in PROX reaction

An experimental investigation is performed into the cleanup of CO in hydrogen for proton exchange membrane fuel cell (PEMFC) using Pt/Al₂O₃ and Ru/Al₂O₃ catalysts. Additionally, the effects of adding the transition metals Co and Fe to a Ru/Al₂O₃ catalyst are examined. The results show that as the level of Pt addition is increased, the maximum CO conversion rate is achieved at a lower temperature. With Ru/Al₂O₃ catalysts, the CO conversion rate increases significantly with increasing Ru addition at temperatures lower than 80 °C For both catalysts, the methane yield increases with increasing temperature and increasing noble metal addition. At temperatures in the range of 100–140 °C, the CO conversion rate and methane yield of the Pt- and Ru-based preferential oxidation (PROX) reactions are both insensitive to the density of the honeycomb carrier. The CO conversion rate is significantly improved by the addition of Fe at temperatures lower than 160 °C and by the addition of Co at temperatures higher than 200 °C. Of the two metals, Fe results in a greater reduction of the methane yield at high temperatures. Finally, both catalysts achieve a stable cleanup performance over the course of a 12-h stability test and suppress the CO concentration to an acceptable level for PEMFC applications.     

Preparation of egg-shell-type Ni/Ru bimetal alumina pellet catalysts: Steam methane reforming for hydrogen production

Egg-shell-type pellet catalysts were prepared by selectively placing nickel and/or ruthenium on the outer region (shell) of alumina pellets so that the active components can be utilized effectively in steam methane reforming (SMR) reaction with high gas-hourly space velocity conditions. To ensure the reproducibility of catalyst preparation, we evaluated two types of commercial alumina pellets. And, we finally selected one commercial alumina pellet, which had uniform pores distribution. The thickness of the ruthenium-shell can be controlled by optimizing the evaporation temperature and rotating speed while preparing an ‘egg-shell-type’ 1 wt. % Ru/alumina catalyst. When applied to a SMR reaction, as the space velocity of the reactant increased in SMR reaction, ‘egg-shell-type’ 1 wt. % Ru/alumina catalyst showed a higher methane conversion than a ‘homo-type’ 1 wt. % Ru/alumina pellet catalyst, in which the active metal was uniformly dispersed in the whole region of pellet. Since ruthenium is a costly noble metal, we prepared a Ni/Ru bimetal catalyst [‘egg-shell-type’ 5 wt. % Ni/0.7 wt. % Ru bimetal catalyst] substituting nickel for some portion of the ruthenium in order to increase the economic feasibility. The bimetal Ni/Ru catalyst showed even better CH₄ conversion than the egg-shell-type catalyst containing ruthenium only. We also confirmed that the egg-shell-type catalyst effectively utilized its active components in the SMR reaction.     

Cathodic hydrogen recovery and methane conversion using Pt coating 3D nickel foam instead of Pt-carbon cloth in microbial electrolysis cells

A cheap but efficient electrode material is required to explore and apply to microbial electrolysis cell (MEC) with high hydrogen evolution reaction (HER) efficiency and low over-potential loss. Pt coating carbon cloth (Pt/CC) was one of the most efficient catalyst for hydrogen production in current lab research, but it is difficult to be applied in practice because of expensive cost and week strength from the base material (carbon cloth). Thus a cheap and effective supporting base material is worth to evaluate on hydrogen recovery and loss to methane for the MEC future application. In this study, nickel foam (NF) was used as an alternative to expensive carbon cloth, and NF coated with Pt (Pt/NF) was applied and evaluated through catalytic performance, hydrogen production efficiency and economic assessment in comparison with Pt/CC. The Pt/NF showed a competitive HER performance to Pt/CC. The highest hydrogen yield was reached 0.71 ± 0.03 m³/m³·d by Pt/NF under 0.8 V, which exceeded 6%, 10% over Pt/CC and NF, respectively. The energy efficiency relative to the electrical energy input was 127% for Pt/NF and 123%, 110% for Pt/CC and NF, respectively. For fifteen cycles, the methane content of Pt/NF got the lowest due to its higher hydrogen evolution activity. The economic analysis showed a 56% reduction when using Pt/NF as supporting base in place of carbon cloth to achieve similar performance. The linear sweep voltammetry (LSV) showed the possibility to further reduce input voltage in a long term operation.     

Electrodeposited Ni–Co–S nanosheets on nickel foam as bioelectrochemical cathodes for efficient H2 evolution

High overpotential and soaring prices of the cathode electrode are the bottlenecks for the development of microbial electrolysis technology for hydrogen production. In this study, a novel one-step electrodeposition method has been attempted to fabricate electrodeposited cathodes in situ growth of Ni–Co–S, Ni–S, Co–S catalyst on nickel foam (NF) to reduce the overpotential of electrodes. Finally, a uniform nanosheet with a high specific surface area and more active sites is formed on the NF surface, resulting in a lower overpotential than plain NF. At 0.8 V, the Co–S/NF cathode produces a favorable 42% increase in hydrogen yield (0.68 m³·m⁻³·d⁻¹), 40% upsurge in current density (10.6 mA/cm³) and 39% rise of cathodic recovery rate (58.0 ± 3.2%) than bare NF, followed by Ni–Co–S/NF and Ni–S/NF cathode. All the electrodeposited electrodes demonstrate enhanced current density and reduced electron losses, thereby achieving efficient hydrogen production. These innovative varieties of electrodes are highly advantageous as they are relatively inexpensive and easy to manufacture with great potential in reducing costs and further real time application in large scale.     

3D-nano-hetero-structured n/n junction,CuO/Ru–ZnO thin films,for hydrogen generation with enhanced photoelectrochemical performances

Hydrogen, derived from solar-water splitting, is a clean and renewable fuel for which per gram energy storage capacity is even higher than fossil fuels. Towards the development of a viable technology for above conversion, this report describes enhanced performance in photoelectrochemical water splitting using uniquely evolved nano-hetero-structured bilayered thin films, CuO/Ru–ZnO as photoanode. Grown over ITO (In:SnO₂) glass substrates by using low-cost and easily up-scalable wet chemical methods, films were characterized for microstructure, optical behaviour and surface characteristics, using XRD and other spectral measurements viz. FESEM, AFM, TEM, UV–Visible Spectroscopy, EDX and XPS. Against monolayered pristine films of CuO and ZnO, bilayered films yielded a major gain in PEC water splitting photocurrent, on being used as working electrode in PEC cell, in conjunction with platinum counter electrode and saturated calomel reference electrode (electrolyte solution 0.1 M NaOH solution, pH 13, temperature 30 ± 3.6 °C). Films with 1% Ru-incorporation yielded highest photocurrent (2.04 mA/cm²). Enhanced photoactivity of bilayered films was found correlated with increments in light absorption, charge carrier density and film surface area, coupled with reduced electrical resistivity. The study highlights an important role played by Ru added in ZnO overlayer, apparently existing as RuO₂ nanoparticles dispersed in ZnO lattice, in hole-transfer from valence band of CuO underlayer to electrolyte, thereby imparting a significant boost on photocurrent generation.     

Methanol electrooxidation at mesoporous Pt and Pt-Ru electrodes: A comparative study with carbon supported materials

The electrochemical behaviour of fuel cell catalysts (mesoporous Pt (MPPt), MPPtRu, MPPt modified by adsorbed Ru (MPPt/Ru) and carbon supported PtRu alloy) was studied using the thin layer flow cell differential electrochemical mass spectrometry (TLFC-DEMS) technique. The catalysts present high catalytic activity towards the methanol oxidation reaction (MOR), being the PtRu/C electrode the least active for MOR, while MPPt/Ru presents higher current densities for this reaction than MPPtRu. The results suggest that the diffusion properties obtained in the porous structure of the MP electrodes and the surface atomic arrangement in the electrode are the main reasons for the higher catalytic activity achieved. Finally, TLFC-DEMS was proved to be a powerful technique which evaluates and correlates the CO₂ efficiency with the catalytic activity and the porous structure of the catalysts.     

Enhanced ethanol production by removal of cutin and epicuticular waxes of wheat straw by plasma assisted pretreatment

The removal of cutin and epicuticular waxes of wheat straw by PAP (plasma assisted pretreatment) was investigated. Wax removal was observed by Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) as chemical change on the surface of most intensively pretreated samples as well as with Scanning Electron Microscopy (SEM) imaging. Compounds resulting from wax degradation were analyzed in the washing water of PAP wheat straw. The wax removal enhanced enzymatic hydrolysis yield and, consequently, the efficiency of wheat straw conversion into ethanol. In total, PAP increased the conversion rate of the raw material carbohydrate content up to 67%, compared to untreated raw material.     

High-performance polypyrrole nanoparticles counter electrode for dye-sensitized solar cells

Polypyrrole (PPy) nanoparticle was synthesized and coated on a conducting FTO glass to construct PPy counter electrode used in dye-sensitized solar cell (DSSC). Scanning electron microscope images show that PPy with porous and particle diameter in 40–60 nm is covered on the FTO glass uniformly and tightly. Cyclic voltammograms of I₂/I⁻ system measurement reveals that the PPy electrode has smaller charge-transfer resistance and higher electrocatalytic activity for the I₂/I⁻ redox reaction than that Pt electrode does. Overall energy conversion efficiency of the DSSC with the PPy counter electrode reaches 7.66%, which is higher (11%) than that of the DSSC with Pt counter electrode. The excellent photoelectric properties, simple preparation procedure and inexpensive cost allow the PPy electrode to be a credible alternative used in DSSCs.     

Crystalline nickel boride nanoparticle agglomerates for enhanced electrocatalytic methanol oxidation

In this paper, crystalline Ni₃B nanoparticle agglomerates have been successfully prepared via dry-powder annealing of the solution-produced amorphous nickel boride. The electron microscopy (EM) images indicate that the Ni₃B nanomaterial is composed of numerous nano-sized particles with a diameter ranging from 100 to 200 nm. The electrocatalytic characteristics of nickel boride in an alkaline medium were observed by cyclic voltammetry (CV) and chronoamperomerty (CA). Compared to the amorphous nickel boride/Ni foam (ANB/NF), the crystalline Ni₃B/Ni foam (CNB/NF) electrode exhibits a higher catalytic performance with low initial oxidation potential of 0.35 V and a high anodic oxidation current density of 62 A g⁻¹ at 0.55 V in a 6 M KOH solution with 0.5 M methanol. And the CNB/NF electrode shows good long-term cycling stability and the catalytic current of methanol retains 87% of the initial value after 1000 time cycles. The CNB/NF electrode should be a promising candidate for alkaline direct methanol fuel cells (DMFCs).     

Metal-organic frameworks supported Ni–Co–S nanosheet arrays for advanced hybrid supercapacitors

Constructing self-supporting porous electrode material with abundant electrochemical active sites can effectively improve the energy storage capacity of supercapacitors. Herein, a novel electrode material (NCS@Co-ZIF/NF) is developed by depositing zeolitic imidazolate frameworks (Co-ZIF) on nickel foams (NF), which is adopted as a precursor (Co-ZIF/NF) to electrodeposit nickel-cobalt sulfides (NCS). The nanosheet arrays with cross-porous structures provide NCS@Co-ZIF/NF with excellent electrochemical characteristics, including a high specific capacity of 144.4 mAh g^?1 at the current density of 1 mA cm^?2, 60.5% capacity retention at 50 mA cm^?2, and superb long-term cycle stability. Furthermore, NCS@Co-ZIF/NF//AC hybrid supercapacitor is fabricated by using NCS@Co-ZIF/NF as positive electrodes and activated carbon (AC) as negative electrodes, which exhibits a high energy density of 33.9 Wh kg^?1 at a power density of 145 W kg^?1.     

Electrodeposited nickel nanocone/NiMoO4 nanocomposite designed as superior electrode materials for high performance supercapacitor

A nickel nanocone-modified NiMoO₄ hybrid (NiMoO₄/NNC) on Ni foam (NF) substrate is engineered to enhance the capacitance performance of NiMoO₄ via facile and convenient electrodeposition strategy, followed by hydrothermal method. The presence of nickel nanocone (NNC) increases the density of reaction active sites of NiMoO₄/NNC/NF, which can shorten the charge diffusion pathway and boost ionic/electronic conductivities. As expected, the NiMoO₄/NNC/NF, as a prospective electrode material, presents appreciable electrochemical properties. Remarkably, the NiMoO₄/NNC/NF electrode demonstrates a high specific capacitance of 2813 F g^?1 at 3 A g^?1 and manifests considerable cycling durability with a retention of 94% of the initial capacitance over consecutive 5000 cycles. Furthermore, a NiMoO₄/NNC/NF//AC/NF asymmetric supercapacitor displays a great electrochemical performance by delivering high energy density (43 Wh kg^?1) and power density (821 W kg^?1) as well as notable durableness (10% decay after 5000 cycles). The presented results suggest that NiMoO₄/NNC/NF can be considered as a binder-free electrode for highly stable supercapacitors.     

Enhanced oxygen evolution reaction activity of NiFe layered double hydroxide on nickel foam- reduced graphene oxide interfaces

Herein, we prepared a novel nickel iron-layered double hydroxide/reduced graphene oxide/nickel foam (NiFe-LDH/RGO/NF) electrodes by two step electrodeposition processes for oxygen evolution reaction (OER). The modification of NF by RGO increased the interface conductivity and electrochemical active surface areas (ECSA) of the electrode. The NiFe-LDH/RGO/NF electrode has shown higher catalytic activity with a lower overpotential of 150 mV at the current density of 10 mA cm⁻². The NiFe-LDH/RGO/NF electrode has also shown a small Tafel slope of 35 mV per decade due to the synergy effect between the larger ECSA and the conductive RGO interface. Furthermore, the electrodes exhibits almost 10 h stability under a general current density of 10 mA cm⁻².     

Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane

Ammonia borane (AB) is an intriguing molecular crystal material with extremely high hydrogen density. In the present study, we prepared ruthenium (Ru) nanoparticles immobilized in montmorillonite (MMT) and examine its catalytic effect on the methanolysis reaction of AB. The Ru/MMT catalyst was prepared by cation-exchange method followed by hydrogen reduction at elevated temperatures. Property examinations found that the Ru/MMT catalyst was highly effective and robust for promoting the methanolysis reaction of AB. For example, the methanolysis system employing Ru/MMT catalyst exhibited an average hydrogen generation rate of 29 L min⁻¹ g⁻¹ (Ru). The catalyst at its twentieth usage retained 95% of its initial activity and ensured 100% conversion of AB. Kinetics studies found that the methanolysis reaction of AB employing Ru/MMT catalyst follows first-order kinetics with respect to AB concentration and catalyst amount, respectively.     

Lowering risk of methanation of carbon support in Ru/carbon catalysts for CO methanation by adding lanthanum

Two series of Ru/C catalysts doped with lanthanum ions are prepared and studied in CO methanation in the H₂-rich gas. The samples are characterized by N₂ physisorption, TG-MS studies, XRD, XPS, TEM/STEM and CO chemisorption. Two graphitized carbons differing in surface area (115 and 80.6 m²/g) are used as supports. The average sizes of ruthenium crystallites deposited on their surfaces are 4.33 and 5.95 nm, respectively. The addition of the proper amount of La to the Ru/carbon catalysts leads to an above 20% increase in the catalytic activity along with stable CH₄ selectivity higher than 99% at all temperatures. Simultaneously, lanthanum acts as the inhibitor of methanation of the carbon support under conditions of high temperature and hydrogen atmosphere. Such positive effects are achieved at a very low concentration of La in the prepared samples, a maximum 0.04 La/Ru (molar ratio). 0.01 mmol La introduced to the Ru/C system leads to 98% CO conversion at 270 °C.