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Ternary nickel-tungsten-copper alloy rivals platinum for catalyzing alkaline hydrogen oxidation.

ABSTRACT: Operating fuel cells in alkaline environments permits the use of platinum-group-metal-free (PGM-free) catalysts and inexpensive bipolar plates, leading to significant cost reduction. Of the PGM-free catalysts explored, however, only a few nickel-based materials are active for catalyzing the hydrogen oxidation reaction (HOR) in alkali; moreover, these catalysts deactivate rapidly at high anode potentials owing to nickel hydroxide formation. Here we describe that a nickel-tungsten-copper (Ni_5.2WCu_2.2) ternary alloy showing HOR activity rivals Pt/C benchmark in alkaline electrolyte. Importantly, we achieved a high anode potential up to 0.3 V versus reversible hydrogen electrode on this catalyst with good operational stability over 20 h. The catalyst also displays excellent CO-tolerant ability that Pt/C catalyst lacks. Experimental and theoretical studies uncover that nickel, tungsten, and copper play in synergy to create a favorable alloying surface for optimized hydrogen and hydroxyl bindings, as well as for the improved oxidation resistance, which result in the HOR enhancement.

SUBMITTER: Qin S

PROVIDER: S-EPMC8113563 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Bimetallic nickel-molybdenum/tungsten nanoalloys for high-efficiency hydrogen oxidation catalysis in alkaline electrolytes.

Project description:Hydroxide exchange membrane fuel cells offer possibility of adopting platinum-group-metal-free catalysts to negotiate sluggish oxygen reduction reaction. Unfortunately, the ultrafast hydrogen oxidation reaction (HOR) on platinum decreases at least two orders of magnitude by switching the electrolytes from acid to base, causing high platinum-group-metal loadings. Here we show that a nickel-molybdenum nanoalloy with tetragonal MoNi4 phase can catalyze the HOR efficiently in alkaline electrolytes. The catalyst exhibits a high apparent exchange current density of 3.41 milliamperes per square centimeter and operates very stable, which is 1.4 times higher than that of state-of-the-art Pt/C catalyst. With this catalyst, we further demonstrate the capability to tolerate carbon monoxide poisoning. Marked HOR activity was also observed on similarly designed WNi4 catalyst. We attribute this remarkable HOR reactivity to an alloy effect that enables optimum adsorption of hydrogen on nickel and hydroxyl on molybdenum (tungsten), which synergistically promotes the Volmer reaction.

| S-EPMC7508880 | biostudies-literature

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

Project description:The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9?V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

| S-EPMC4980487 | biostudies-literature

Platinum-copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis.

Project description:Selective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 103 molglycerol·molPtCu-SAA-1·h-1, which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu-SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C-H bond whilst the terminal C-O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu-SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

| S-EPMC6925196 | biostudies-literature

Nitrogen-Tungsten Oxide Nanostructures on Nickel Foam as High Efficient Electrocatalysts for Benzyl Alcohol Oxidation.

Project description:Electrocatalytic alcohol oxidation (EAO) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts is a major challenge. Herein, we developed a nitrogen-doped bimetallic oxide electrocatalyst (WO-N/NF) by a one-step hydrothermal method for the selective electrooxidation of benzyl alcohol to benzoic acid in alkaline electrolytes. The WO-N/NF electrode features block-shaped particles on a rough, inhomogeneous surface with cracks and lumpy nodules, increasing active sites and enhancing electrolyte diffusion. The electrode demonstrates exceptional activity, stability, and selectivity, achieving efficient benzoic acid production while reducing the electrolysis voltage. A low onset potential of 1.38 V (vs. RHE) is achieved to reach a current density of 100 mA cm-2 in 1.0 M KOH electrolyte with only 0.2 mmol of metal precursors, which is 396 mV lower than that of water oxidation. The analysis reveals a yield, conversion, and selectivity of 98.41%, 99.66%, and 99.74%, respectively, with a Faradaic efficiency of 98.77%. This work provides insight into the rational design of a highly active and selective catalyst for electrocatalytic alcohol oxidation.

| S-EPMC11357156 | biostudies-literature

Transcriptomic profiling of HSkMC cells exposed to tungsten alloy particles 2

Project description:Human skeletal muscle cell cultures (HSkMC) were exposed to particles of various tungsten alloys or tantalum and transcriptomic responses after 24 hours were determined by gene expression microarrays in comparison with untreated control cultures.

2015-03-01 | E-MTAB-2993 | biostudies-arrayexpress

Transcriptomic profiling of HSkMC cells exposed to tungsten alloy particles 1

2015-03-01 | E-MTAB-2991 | biostudies-arrayexpress

Alkaline Ethanol Oxidation Reaction on Carbon Supported Ternary PdNiBi Nanocatalyst using Modified Instant Reduction Synthesis Method.

Project description:Direct ethanol fuel cells (DEFC) still lack active and efficient electrocatalysts for the alkaline ethanol oxidation reaction (EOR). In this work, a new instant reduction synthesis method was developed to prepare carbon supported ternary PdNiBi nanocatalysts with improved EOR activity. Synthesized catalysts were characterized with a variety of structural and compositional analysis techniques in order to correlate their morphology and surface chemistry with electrochemical performance. The modified instant reduction synthesis results in well-dispersed, spherical Pd85Ni10Bi5 nanoparticles on Vulcan XC72R support (Pd85Ni10Bi5/C(II-III)), with sizes ranging from 3.7 ± 0.8 to 4.7 ± 0.7 nm. On the other hand, the common instant reduction synthesis method leads to significantly agglomerated nanoparticles (Pd85Ni10Bi5/C(I)). EOR activity and stability of these three different carbon supported PdNiBi anode catalysts with a nominal atomic ratio of 85:10:5 were probed via cyclic voltammetry and chronoamperometry using the rotating disk electrode method. Pd85Ni10Bi5/C(II) showed the highest electrocatalytic activity (150 mA⋅cm-2; 2678 mA⋅mg-1) with low onset potential (0.207 V) for EOR in alkaline medium, as compared to a commercial Pd/C and to the other synthesized ternary nanocatalysts Pd85Ni10Bi5/C(I) and Pd85Ni10Bi5/C(III). This new synthesis approach provides a new avenue to developing efficient, carbon supported ternary nanocatalysts for future energy conversion devices. Graphical AbstractThe modified instant reduction method for synthesis of ternary Pd85Ni10Bi5/C(II) nanocatalyst using Vulcan XC72R as carbon support initiates an agglomeration reduction, provides low average particle size, and enables enhanced activity for the alkaline ethanol oxidation reaction (EOR) compared to the common instant reduction method and to a commercial Pd/C catalyst.

| S-EPMC7683445 | biostudies-literature

Enhancing the Hydrogen Evolution Reaction Activity of Platinum Electrodes in Alkaline Media Using Nickel-Iron Clusters.

Project description:Herein, we demonstrate an easy way to improve the hydrogen evolution reaction (HER) activity of Pt electrodes in alkaline media by introducing Ni-Fe clusters. As a result, the overpotential needed to achieve a current density of 10 mA cm-2 in H2 -saturated 0.1 m KOH is reduced for the model single-crystal electrodes down to about 70 mV. To our knowledge, these modified electrodes outperform any other reported electrocatalysts tested under similar conditions. Moreover, the influence of 1) Ni to Fe ratio, 2) cluster coverage, and 3) the nature of the alkali-metal cations present in the electrolyte on the HER activity has been investigated. The observed catalytic performance likely originates from both the improved water dissociation at the Ni-Fe clusters and the subsequent optimal hydrogen adsorption and recombination at Pt atoms present at the Ni-Fe/Pt boundary.

| S-EPMC7318285 | biostudies-literature

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

Project description:The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

| S-EPMC4735558 | biostudies-literature

Bimetallic nickel/manganese phosphate-carbon nanofiber electrocatalyst for the oxidation of formaldehyde in alkaline medium.

Project description:The development of earth-abundant transition metal-based catalysts, supported by a conductive carbonaceous matrix, has received great attention in the field of conversion of formaldehyde derivatives into toxic-free species. Herein, we report a comprehensive investigation of bimetallic electrocatalyst activity towards the electrooxidation of formaldehyde. The bimetallic phosphate catalyst is prepared by co-precipitation of Ni and Mn phosphate precursors using a simple reflux approach. Then the bimetallic catalyst is produced by mixing the Ni/Mn with carbon fibres (CNFs). The structural properties and crystallinity of the catalyst were investigated by using several techniques, such as scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, and Brunauer Emmett-Teller theory. The system performance was studied under potentiostatic conditions. Some theoretical thermodynamic and kinetic models were applied to assess the system performance. Accordingly, key electrochemical parameters, including surface coverage (Γ) of active species, charge transfer rate (k s), diffusion coefficient of the formaldehyde (D), and catalytic rate constant (k cat) were calculated at Γ = 1.690 × 10-4 mmol cm-2, k s = 1.0800 s-1, D = 1.185 × 10-3 cm2 s-1 and k cat = 1.08 × 105 cm3 mol-1 s-1. These findings demonstrate the intrinsic electrocatalytic activity of formaldehyde electrooxidation on nickel/manganese phosphate- CNFs in alkaline medium.

| S-EPMC9292137 | biostudies-literature

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