Enhanced oxygen evolution reaction kinetics through biochar-based nickel-iron phosphides nanocages in water electrolysis for hydrogen production

Highly-efficient and stable non-noble metal electrocatalysts for overcoming the sluggish kinetics of oxygen evolution reaction (OER) is urgent for water electrolysis. Biomass-derived biochar has been considered as promising carbon material because of its advantages such as low-cost, renewable, simple preparation, rich structure, and easy to obtain heteroatom by in-situ doping. Herein, Ni₂P–Fe₂P bimetallic phosphide spherical nanocages encapsulated in N/P-doped pine needles biochar is prepared via a simple two-step pyrolysis method. Benefiting from the maximum synergistic effects of bimetallic phosphide and biochar, high conductivity of biochar encapsulation, highly exposed active sites of Ni₂P–Fe₂P spherical nanocages, rapid mass transfer in porous channels with large specific surface area, and the promotion in adsorption of reaction intermediates by high-level heteroatom doping, the (Ni_0.75Fe_0.25)₂P@NP/C demonstrates excellent OER activity with an overpotential of 250 mV and a Tafel slope of 48 mV/dec at 10 mA/cm² in 1 M KOH. Also it exhibits a long-term durability in 10 h electrolysis and its activity even improves during the electrocatalytic process. The present work provides a favorable strategy for the inexpensive synthesis of biochar-based transition metal electrocatalysts toward OER, and improves the water electrolysis for hydrogen production.     

Spinel CoFe2O4 /carbon nanotube composites as efficient bifunctional electrocatalysts for oxygen reduction and oxygen evolution reaction

In the development of fuel cells, it is the key to large-scale commercialization of fuel cells to rationally design and synthesize efficient and non-noble metals-based bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In this paper, spinel CoFe₂O₄/carbon nanotube composites (CoFe₂O₄/CNTs/FA) were synthesized by solvothermal and calcination method. XRD, TEM, XPS and BET characterizations indicate that the addition of complexing agent fumaric acid can improve the crystal growth kinetics and morphology of CoFe₂O₄/CNTs nanohybirds. The as-synthesized CoFe₂O₄/CNTs/FA pyrolyzed at 500 °C have an outstanding bifunctional catalytic activity for ORR and OER with the potential of 1.62V (vs. RHE) at a current density of 10 mA/cm² and half-wave potential E_1/2 = 0.808V (vs. RHE) in alkaline electrolyte, respectively. It is obviously better than unloaded CoFe₂O₄ nanoparticles and commercial CNTs. CoFe₂O₄/CNTs/FA also exhibit better methanol tolerance ability and durability than commercial Pt/C and RuO₂ catalyst. This investigation broadens an idea of simple compounding of spinel with carbon-based materials to improve electrochemical properties.     

Homogeneously dispersed cobalt/iron electrocatalysts with oxygen vacancies and favorable hydrophilicity for efficient oxygen evolution reaction

Rational design of highly conductive and hydrophilic electrocatalysts are extremely important to promote their oxygen evolution reaction (OER). In this work, a homogeneously dispersed carbon-based cobalt/iron catalyst (Co/Fe–C) with abundant oxygen vacancies and favorable hydrophilicity is fabricated via a facile metal-polyphenol complexes strategy. The tannic acid (TA) and fulvic acid (FA) derived 0.3 Co/Fe–C catalysts show greatly similar morphologies, as well as the performance optimization process of electrocatalytic OER. Specifically, the TA-derived 0.3 Co/Fe–C catalyst exhibits an overpotential of 284 mV at 10 mA cm^?2 for OER in alkaline electrolyte. Combined a series of characterization techniques suggest that abundant oxygen vacancies and favorable surface hydrophilicity can improve electronic conductivity of the catalyst and accelerate reactant adsorption and charge transfer rate on the catalyst surface, thus promoting OER activity of the catalysts. This study might provide a new perspective to construct advanced electrocatalysts with oxygen vacancies and hydrophilic surface for electrocatalytic applications.     

Nonwoven Ni–NiO/carbon fibers for electrochemical water oxidation

The development of technologically efficient anodes for water oxidation is crucial to improve hydrogen production via water splitting. Electrodes based on metallic active sites dispersed in carbon matrices have been shown to be an attractive way to attain this goal. However, challenges remain to prevent catalyst agglomeration that otherwise can result in a decrease of performance over time.In this work, we report an alternative and efficient method to produce nickel-nickel oxide nanoparticles-embedded in carbon nanofibers (Ni–NiO/C), by the solution blow spinning (SBS) process. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses show the carbon nanofibrillar matrix as a robust support, with well-dispersed nickel nanoparticles on the surface. The responses of the linear scanning voltammetry, cyclic voltammetry and electrochemical impedance spectroscopy demonstrate how a small fraction of nickel on the fiber surface (≈1.2–5.3%) is enough to promote substantial improvement in performance (η = 278 and 309 mV vs RHE for 10 mA cm^?2) and a significant turnover frequency (TOF) values of 1.38 (η = 278) and 1.30 s^?1 (η = 309). These promising results are correlated with a large amount of Ni³⁺ present on the fiber surfaces, as identified by X-ray Photoelectron Spectroscopy (XPS). This work provides a low-cost and rapid preparation technique that can be extended for the manufacture of a wide variety of electrodes based on metals supported on carbon nanofibers.     

Morphological engineering of carbon-based materials: in the quest of efficient catalysts for overall water splitting

This work attempts to optimize the catalytic activity of the carbon-based materials by engineering their morphological structure. Several flake-like quantum dots with different shapes such as triangulene, elliptical, rhomboid, and square, as well as hydrocarbons having sunflower, kekulene, and snow-like structures, are considered and their electrocatalytic activities toward the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are theoretically evaluated. The activity analysis indicates that the OER overpotentials for the examined carbon materials vary in the range between 0.56 and 1.22 V. Benefiting from the improved electronic properties due to the proper morphology, remarkable catalytic activity was achieved for the snow-like morphology affording overpotentials of 0.56 V for OER and ?0.05 V for HER. In addition to snow-like, other morphologies such as triangulene and square can effectively promote acidic hydrogen evolution via Volmer-Heyrovsky mechanism. On contrary, the high values of free energies for H₂O dissociation step reveal that, under the alkaline condition, the examined carbon materials cannot be considered as efficient HER catalysts.     

Ni doped Bi2WO6 for electrochemical OER activity

Due to over depletion of fossil fuels, researchers started to find hydrogen energy to compete with the energy demands. Bi₂WO₆ and Ni (5% and 10%) doped Bi₂WO₆ were prepared via hydrothermal route. Structural confirmation of undoped and doped Bi₂WO₆ nanostructures was estimated by using standard characterization studies. The nanoflake and nanoneedle like morphology of undoped and Ni doped Bi₂WO₆ was confirmed in nanoscale range. The highest OER activity was achieved for 10% Ni doped Bi₂WO₆ nanostructure electrode with the excellent current density of 272 mA/g with overpotential of 242 mV in the fabricated three electrode half cell set up. The higher electron transport offered by Ni ions to Bi₂WO₆ host has been reported with the electrochemical mechanism. Hence, the unusual robust electrodes for electrochemical potential applications by tuning its property via suitable foreign ion dopant could be the great beginning of this recent year research. In such a way, this work would be the better way of swapping of nobel metal catalysts for electrochemical OER activity.     

Efficient overall water splitting using nickel boride-based electrocatalysts

Currently there is tremendous interest in the discovery of low cost and efficient electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). In this work, iron-doped nickel boride (Fe_xNi_1-xB) and nickel boride (NiB) were successfully grown on 3D self-supporting graphene (SSG) electrodes via a one-step reduction approach. The Fe_0.2Ni_0.8B/SSG electrode required a very low overpotential of only 263 mV for OER (the best OER activity achieved to date for a metal boride). NiB/SSG showed modest OER performance but excellent HER activity. A water electrolyzer comprising Fe_0.2Ni_0.8B/SSG and NiB/SSG delivered a current density of 10 mA cm⁻² at a voltage of only 1.62 V. Further, the Fe_0.2Ni_0.8B/SSG and NiB/SSG catalysts showed excellent stability with no deactivation observed over 14 h of testing. Results demonstrate that nickel boride-based electrocatalysts are promising lost cost alternatives to precious metal-based electrocatalysts for OER, HER and overall water splitting.     

Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Construction of hierarchical Prussian Blue Analogue phosphide anchored on Ni2P@MoOx nanosheet spheres for efficient overall water splitting

In response to the energy crisis, molybdenum-based catalyst has been proposed as a high-performance electrocatalytic material due to its low price and excellent HER performance. However, in contrast with its excellent HER performance, its poor OER performance often limits practical application as a high-performance overall water splitting catalyst. In this study, Prussian blue analogue (PBA) is grown in-situ on molybdenum-based nanosheet spheres by a simple and ingenious method and then subjected to phosphorization. The resulting composite catalyst exhibits highly efficient overall water splitting performance, overpotentials at current densities of 10 mA cm⁻² and 100 mA cm⁻² for the HER and OER are −61 mV and 268 mV, respectively. Moreover, an alkaline electrolyzer makes up by the catalyst both as positive and negative can reach a cell voltage 1.494 V at 10 mA cm⁻² for the overall water splitting. This method has provided a new strategy to effective combine PBA and molybdenum-based catalyst.