Nanostructured Nickel Nitride with Reduced Graphene Oxide Composite Bifunctional Electrocatalysts for an Efficient Water-Urea Splitting.
ABSTRACT: A three-dimensional nickel nitride with reduced graphene oxide composite on nickel foam (s-X, where s represents Ni3N/rGO@NF and the annealing temperature X can be 320, 350, or 380) electrode has been fabricated through a facile method. We demonstrate that s-350 has excellent urea oxidation reaction (UOR) activity, with a demanded potential of 1.342 V to reach 10 mA/cm2 and bears high hydrogen evolution reaction (HER) activity. It provides a low overpotential of 124 mV at 10 mA/cm2, which enables the successful construction of its two-electrode alkaline electrolyzer (s-350||s-350) for water-urea splitting. It merely requires a voltage of 1.518 V to obtain 100 mA/cm2 and is 0.145 V lower than that of pure water splitting. This noble metal-free bifunctional electrode is regarded as an inexpensive and effective water-urea electrolysis assisted hydrogen production technology, which is commercially viable.
Project description:Commercial hydrogen production by electrocatalytic water splitting will benefit from the realization of more efficient and less expensive catalysts compared with noble metal catalysts, especially for the oxygen evolution reaction, which requires a current density of 500 mA/cm2 at an overpotential below 300 mV with long-term stability. Here we report a robust oxygen-evolving electrocatalyst consisting of ferrous metaphosphate on self-supported conductive nickel foam that is commercially available in large scale. We find that this catalyst, which may be associated with the in situ generated nickel-iron oxide/hydroxide and iron oxyhydroxide catalysts at the surface, yields current densities of 10 mA/cm2 at an overpotential of 177 mV, 500 mA/cm2 at only 265 mV, and 1,705 mA/cm2 at 300 mV, with high durability in alkaline electrolyte of 1 M KOH even after 10,000 cycles, representing activity enhancement by a factor of 49 in boosting water oxidation at 300 mV relative to the state-of-the-art IrO2 catalyst.
Project description:Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180?mV at a current density of 10?mA?cm-2. The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.
Project description:Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500?mA?cm(-2)) at low applied potentials. Here we show that an efficient oxygen electrode can be developed by electrodepositing amorphous mesoporous nickel-iron composite nanosheets directly onto macroporous nickel foam substrates. The as-prepared oxygen electrode exhibits high catalytic activity towards water oxidation in alkaline solutions, which only requires an overpotential of 200?mV to initiate the reaction, and is capable of delivering current densities of 500 and 1,000?mA?cm(-2) at overpotentials of 240 and 270?mV, respectively. The electrode also shows prolonged stability against bulk water electrolysis at large current. Collectively, the as-prepared three-dimensional structured electrode is the most efficient oxygen evolution electrode in alkaline electrolytes reported to the best of our knowledge, and can potentially be applied for industrial scale water electrolysis.
Project description:Water splitting is thermodynamically uphill reaction, hence it cannot occur easily, and also highly complicated and challenging reaction in chemistry. In electrocatalytic water splitting, the combination of oxygen and hydrogen evolution reactions produces highly clean and sustainable hydrogen energy and which attracts research communities. Also, fabrication of highly active and low cost materials for water splitting is a major challenge. Therefore, in the present study, ?-Fe2O3 nanowires were fabricated from highly available and cost-effective iron plate without any chemical modifications/doping onto the surface of the working electrode with high current density. The fabricated nanowires achieved the current density of 10?mA/cm2 at 1.88?V vs. RHE with the scan rate of 50?mV/sec. Stability measurements of the fabricated Fe2O3 nanowires were monitored up to 3275?sec with the current density of 9.6?mA/cm2 at a constant potential of 1.7?V vs. RHE and scan rate of 50?mV/sec.
Project description:Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel-vanadium-layered double hydroxide that shows a current density of 27?mA?cm(-2) (57?mA?cm(-2) after ohmic-drop correction) at an overpotential of 350?mV for water oxidation. Such performance is comparable to those of the best-performing nickel-iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel-vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting.
Project description:Herein, we report an iron/nickel/zinc mixed oxide as a catalyst for the electrochemical water oxidation. This catalyst was synthesized by a straightforward method for the synthesis of an iron/nickel/zinc mixed oxide through the calcination of a Fe/Ni/Zn organometallic compound. The calcined product contains Fe and Ni as crucial ions for water oxidation, accompanied by the presence of Zn ions. The removal of Zn ions from the mixed oxide provides more active sites on the surface of the catalyst. The composition of the compound was characterized by some common methods and found to be an efficient water-oxidizing catalyst. The catalyst on FTO at pH?=?13 yields a current density of 12?mA/cm2 at 1.2?V (vs. Ag?AgCl). After 5?hours at 1.1?V, the electrode not only shows no decrease in performance, but also shows an increase from 4 to 7?mA/cm2 in the water oxidation activity. Tafel plot, for the electrode at pH?=?13 in KOH solution (0.1?M) showed linearity for the graph of lg j vs. V with both relatively low (220.4?mV per decade) and high overpotentials (903.7?mV per decade).
Project description:The development of non-noble metal catalysts for hydrogen revolution in alkaline media is highly desirable, but remains a great challenge. Herein, synergetic ultrathin NiO/MoS2 catalysts were prepared to improve the sluggish water dissociation step for HER in alkaline conditions. With traditional electrode assembly methods, MoS2:NiO-3:1 exhibited the best catalytic performance; an overpotential of 158 mV was required to achieve a current density of 10 mA/cm2. Further, a synergetic ultrathin NiO/MoS2/nickel foam (NF) electrode was assembled by electrophoretic deposition (EPD) and post-processing reactions. The electrode displayed higher electrocatalytic ability and stability, and an overpotential of only 121 mV was needed to achieve a current density of 10 mA/cm2. The improvement was ascribed to the better catalytic environment, rather than a larger active surface area, a higher density of exposed active sites or other factors. DFT calculations indicated that the hybrid NiO/MoS2 heterostuctured interface is advantageous for the enhanced water dissociation step and the corresponding lower kinetic energy barrier-from 1.53 to 0.81 eV.
Project description:Great attention has been focused on the design of electrocatalysts to enable electrochemical water splitting-a technology that allows energy derived from renewable resources to be stored in readily accessible and non-polluting chemical fuels. Herein we report a bifunctional nanotube-array electrode for water splitting in alkaline electrolyte. The electrode requires the overpotentials of 58 mV and 184 mV for hydrogen and oxygen evolution reactions respectively, meanwhile maintaining remarkable long-term durability. The prominent performance is due to the systematic optimization of chemical composition and geometric structure principally-that is, abundant electrocatalytic active sites, excellent conductivity of metallic 1T' MoS2, synergistic effects among iron, cobalt, nickel ions, and the superaerophobicity of electrode surface for fast mass transfer. The electrode is also demonstrated to function as anode and cathode, simultaneously, delivering 10 mA cm-2 at a cell voltage of 1.429 V. Our results demonstrate substantial improvement in the design of high-efficiency electrodes for water electrolysis.
Project description:In the development of photoelectrochemical cells for water splitting or CO2 reduction, a major challenge is O2 evolution at photoelectrodes that, in behavior, mimic photosystem II. At an appropriate semiconductor electrode, a water oxidation catalyst must be integrated with a visible light absorber in a stable half-cell configuration. Here, we describe an electrode consisting of a light absorber, an intermediate electron donor layer, and a water oxidation catalyst for sustained light driven water oxidation catalysis. In assembling the electrode on nanoparticle SnO2/TiO2 electrodes, a Ru(II) polypyridyl complex was used as the light absorber, NiO was deposited as an overlayer, and a Ru(II) 2,2'-bipyridine-6,6'-dicarboxylate complex as the water oxidation catalyst. In the final electrode, addition of the NiO overlayer enhanced performance toward water oxidation with the final electrode operating with a 1.1 mA/cm2 photocurrent density for 2 h without decomposition under one sun illumination in a pH 4.65 solution. We attribute the enhanced performance to the role of NiO as an electron transfer mediator between the light absorber and the catalyst.
Project description:In this work, the plating of high-quality amorphous nickel-phosphorous coating with low resistivity of 0.45 µΩ m (298 K) on complex 3D printed polymeric structures with high uniformity is reported. Such a polymer metallization results in an effective conductivity of 4.7 × 104 S m-1. This process also allows flexible structures to maintain their flexibility along with the conductivity. Octet-truss structures with nickel-iron-(oxo) hydroxide nanosheets electrodeposited onto further displays excellent water-splitting performance as catalytic electrodes, i.e., in KOH (1 m, aq), a low oxygen evolution reaction (OER) overpotential of 197 mV at 10 mA cm-2 and Tafel slope of 51 mV dec-1. Using this light-weight electrode with high specific area, strength, and corrosion resistance properties, a fully functional water-splitting system is designed and fabricated through the concentric integration of 3D printed components. A dense polymeric mesh implemented is also demonstrated as an effective separator of hydrogen and oxygen bubbles in this system.