Electrochemical water splitting presents an optimal approach for generating hydrogen ( H2), a highly promising alternative energy source. Nevertheless, the slow kinetics of the electrochemical oxygen evolution reaction (OER) and the exorbitant cost, limited availability, and susceptibility to oxidation of noble metal-based electrocatalysts have compelled scientists to investigate cost-effective and efficient electrocatalysts. Bimetallic nanostructured materials have been demonstrated to exhibit improved catalytic performances for the oxygen evolution reaction (OER). Herein, we report carbon aerogel (CA) decorated with different molar ratios of Fe and Ni with enhanced OER activity. Microwave irradiation was involved as a novel strategy during the synthesis process. Inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscope (SEM), Energy dispersive X-ray spectroscopy (EDAX spectra and EDAX mapping), Transmission Electron Microscope (TEM), High-Resolution Transmission Electron Microscope (HR-TEM), and Selected Area Electron Diffraction (SAED) were used for physical characterizations of as-prepared material. Electrochemical potential towards OER was examined through cyclic voltammetry (CV), chronoamperometry, and electrochemical impedance spectroscopy (EIS). The FeNi/CA with optimized molar ratios exhibits low overpotential 377 mV at 10 mAcm− 2, smaller Tafel slope (94.5 mV dec− 1), and high turnover frequency (1.09 s− 1 at 300 mV). Other electrocatalytic parameters were also calculated and compared with previously reported OER catalysts. Additionally, chronoamperometric studies confirmed excellent electrochemical stability, as the OER activity shows minimal change even after a stability test lasting 3600 s. Moreover, the bimetallic (Fe and Ni) carbon aerogel exhibits faster catalytic kinetics and higher conductivity than the monometallic (Fe), which was observed through EIS investigation. This research opens up possibilities for utilizing bi- or multi-metallic anchored carbon aerogel with high conductivities and exceptional electrocatalytic performances in electrochemical energy conversion.
Exploring cheap and efficient oxygen evolution reaction (OER) catalysts is extremely vital for the commercial application of advanced energy storage and conversion systems. Herein, a self-supporting Co3S4/ S-doped reduced graphene oxide ( Co3S4/S-rGO) film catalyst is successfully prepared by a blade coating coupled with high-temperature annealing strategy, and its morphology, structure and composition are measured and analyzed. It is substantiated that the as-synthesized Co3S4/ S-rGO film possesses unique self-supporting structure, and is composed of uniformly dispersed Co3S4 nanoparticles and highly conductive S-rGO, which benefit the exposure of catalytic sites and electron transfer. By reason of the synergistic effect of the two individual components, the self-supporting Co3S4/ S-rGO film catalyst displays outstanding catalytic performance towards OER. As a consequence, the Co3S4/ S-rGO film catalyst delivers an overpotential of 341 mV at 10 mA cm-2, and the current attenuation rate is only 2.6% after continuous operation for 4 h, verifying excellent catalytic activity and durability. Clearly, our results offers a good example for the construction of high-performance self-supporting carbon-based composite film catalysts for critical electrocatalytic reactions.
A novel kind of self-assembled graphene quantum dots-Co3O4 (GQDs-Co3O4) nanocomposite was successfully manufactured through a hydrothermal approach and used as an extremely effectual oxygen evolution reaction (OER) electrocatalyst. The characterization of morphology with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that Co3O4 nanosheets combined with graphene quantum dots (GQDs) had a new type of hexagonal lamellar selfassembly structure. The GQDs-Co3O4 electrocatalyst showed enhanced electrochemical catalytic properties in an alkaline solution. The start potential of the OER was 0.543 V (vs SCE) in 1 M KOH solution, and 0.577 V (vs SCE) in 0.1 M KOH solution correspondingly. The current density of 10 mA cm− 2 had been attained at the overpotential of 321 mV in 1 M KOH solution and 450 mV in 0.1 M KOH solution. Furthermore, the current density can reach 171 mA cm− 2 in 1 M KOH solution and 21.4 mA cm− 2 in 0.1 M KOH solution at 0.8 V. Moreover, the GQDs-Co3O4 nanocomposite also maintained an ideal constancy in an alkaline solution with only a small deterioration of the activity (7%) compared with the original value after repeating potential cycling for 1000 cycles.
Exploring earth-abundant, highly effective and stable electrocatalysts for electrochemical water splitting is urgent and essential to the development of hydrogen (H2) energy technology. Iron-cobalt layered double hydroxide (FeCo-LDH) has been widely used as an electrocatalystfor OER due to its facile synthesis, tunable components, and low cost. However, LDH synthesized by the traditional hydrothermal method tends to easily agglomerate, resulting in an unstable structure that can change or dissolve in an alkaline solution. Therefore, studying the real active phase is highly significant in the design of electrochemical electrode materials. Here, metal-organic frameworks (MOFs) are used as template precursors to derive FeCo-LDH from different iron sources. Iron salts with different anions have a significant impact on the morphology and charge transfer properties of the resulting materials. FeCo-LDH synthesized from iron sulfate solution (FeCo-LDH-SO4) exhibits a hybrid structure of nanosheets and nanowires, quite different from other electrocatalysts that were synthesized from iron chloride and iron nitrate solutions. The final FeCo-LDH-SO4 had an overpotential of 247 mV with a low Tafel-slope of 60.6 mV dec-1 at a current density of 10 mA cm-2 and delivered a long-term stability of 40 h for the OER. This work provides an innovative and feasible strategy to construct efficient electrocatalysts.
The development of heteroatoms doped inorganic nanocrystal-carbon composites (INCCs) has attained a great focus for energy applications (energy production and energy storage). A precise approach to fabricate the INCCs with homogenous distribution of the heteroatoms with an appropriate distribution of metal atoms remains a challenge for material scientists. Herein, we proposed a facile two-step route to synthesize INCC with doping of metal (α-Fe2O3) and non-metals (N, P, O) using hydrogel formed by treating hexachlorocyclotriphosphazene (HCCP) and 3, 4, 5-trihydroxy benzoic acid (Gallic acid). Metal oxide was doped using an extrinsic doping approach by varying its content and non-metallic doping by an intrinsic doping approach. We have fabricated four different samples (INCC-0.5%, INCC-1.0%, INCC-1.5%, and INCC-2.0%), which exhibit the uniform distribution of the N, P, O, and α-Fe2O3 in the carbon architecture. These composite materials were applied as anode material in water oxidation catalysis (WOC); INCC-1.5% electro-catalyst confirmed by cyclic voltammetry (CV) with a noticeable catholic peak 0.85 V vs RHE and maximal current density 1.5 mA.cm−2. It also delivers better methanol tolerance and elongated stability than RuO2; this superior performance was attributed due to the homogenous distribution of the α-Fe2O3 causing in promotion of adsorption of O2 initially and a greater surface area of 1352.8 m2/ g with hierarchical pore size distribution resulting higher rate of ion transportation and mass-flux.
Hydrogen energy is a promising source of renewable and clean energy for various industries, such as chemical, automobile, and energy industries. Electrolysis of water is one of the basic methods for the production of hydrogen energy. However, the high overpotential of the oxygen evolution reaction (OER) in water electrolysis has hindered the effective production of hydrogen using this method. Thus, the development of high-efficiency non-precious metal-based electrocatalysts for OER is extremely significant. In this study, we adopted a one-step hydrothermal method to fabricate Ni-based catalysts with N/Sdual doped graphene oxide/carbon nanotube (GO/CNT) supports using thiourea ( CH4N2S) and urea as the S source and the N source. It was observed that the amount of thiourea utilized in the synthesis of the catalyst affected the morphology, composition, and the electrochemical properties of the catalyst. For a GO/CNT-to-thiourea mass ratio of 1:10, the catalyst exhibited the highest activity, where the OER overpotential was 320 mV at a current density of 10 mA/cm2. This was attributed to the high specific surface area, high conductivity, and fast electron transport channels of the N/S-dual doped GO/ CNT composite. Furthermore, sulfurization of the Ni particles to form nickel sulfide played a significant role in enhancing the catalytic performance.
The oxygen evolution reaction (OER) is very sluggish compared to the hydrogen evolution reaction (HER). Considering this difference is essential when designing and developing a cost-effective and facile synthesis method for a catalyst that can effectively perform OER activity. The material should possess a high surface area and more active sites. Considering these points, in this work we successfully synthesized sheets of cobalt phosphate hydrate (CP) and sulphurated cobalt phosphate hydrate (CPS) material, using simple successive ionic layered adsorption and reaction (SILAR) methods followed by sulfurization. The CP and CPS electrodes exhibited overpotentials of 279 mV with a Tafel slope of 212 mV dec1 and 381 mV with a Tafel slope of 212 mV dec1, respectively. The superior performance after sulfurization is attributed to the intrinsic activity of the deposited well-aligned nanosheet structures, which provided a substantial number of electrochemically active surface sites, speeded electron transfer, and at the same time improved the diffusion of the electrolyte.
Environmental issues such as global warming due to fossil fuel use are now major worldwide concerns, and interest in renewable and clean energy is growing. Of the various types of renewable energy, green hydrogen energy has recently attracted attention because of its eco-friendly and high-energy density. Electrochemical water splitting is considered a pollution-free means of producing clean hydrogen and oxygen and in large quantities. The development of non-noble electrocatalysts with low cost and high performance in water splitting has also attracted considerable attention. In this study, we successfully synthesized a NiCo2O4/NF electrode for an oxygen evolution reaction in alkaline water splitting using a hydrothermal method, which was followed by post-heat treatment. The effects of heat treatment on the electrochemical performance of the electrodes were evaluated under different heat-treatment conditions. The optimized NCO/NF-300 electrode showed an overpotential of 416 mV at a high current density of 50 mA/cm2 and a low Tafel slope (49.06 mV dec-1). It also showed excellent stability (due to the large surface area) and the lowest charge transfer resistance (12.59 Ω). The results suggested that our noble-metal free electrodes have great potential for use in developing alkaline electrolysis systems.
Electrochemical water splitting is an important process for next generation of eco-friendly energy systems. The oxygen evolution reaction (OER), which occurs at an anode during the process, requires efficient electrocatalysts to reduce activation energies. Although Ru- or Ir-containing materials show excellent electrocatalytic activities, their high cost is a critical drawback. Consequently, the development of efficient electrocatalysts composed of low-cost metal components is a great challenge. In this study, we develop a new route to produce a hybrid material (Fe–NC) containing Fe3C particles dispersed on the surface of N-doped carbon (NC) materials by heat treatment of a mixture of urea and Fe(II)Cl2(H2O)4. Microscopic analyses prove that the Fe3C particles are placed on the surfaces of thin NC materials. Additionally, various characterizations reveal that the particles contain Fe3C structure. Fe–NC shows good electrocatalytic properties with onset and overpotentials of 1.57 V and 545 mV, respectively, for OER in KOH electrolyte. This study suggests the possibility of the use of Fe3C- based composites as OER electrocatalysts.
Nitrogen-doped carbon dots (N-CDs), derived from the biomass (anthocyanin), are the novel additive to the nanocarbon materials, which is expected to bring a wide spectrum of novel applications. Moreover, metallic oxides are emerging for their unique potential for electrocatalysis. Herein, we report the synthesis of N-CDs for the selective detection of Fe3+ with a limit of detection of 2.57 μM in the range of 5–60 μM using ethylenediamine and H2O2 by a hydrothermal method. The obtained N-CDs displayed a spherical morphology with a particle size range of 2–7 nm and emitted blue luminescence at 394 nm under excitation at 319 nm. Meanwhile, we have demonstrated the fabrication of cost-efficient electrocatalysts for oxygen evolution reaction (OER) in an alkaline medium, employing N-CDs. Owing to the successful incorporation of N-CDs into NiO nanospheres, the resulting N-CDs/NiO with large surface areas, fast charge transfer, and increased conductivity vastly improved the catalytic activity. Remarkably, the optimal of N-CDs/NiO composite requires the overpotential of only 380 mV at a current density of 10 mA cm− 2 and a relatively low Tafel slope of 57.96 mV dec− 1 compared with pure NiO. These results open up a facile route for the application of N-CDs and offer prospects for CD-metal hybrids as high OER catalysts in electrochemical energy devices.
Oxygen evolution reaction (OER) is an essential step at an anode in electrochemical water-splitting process and requires efficient electrocatalysts to reduce overpotentials. Although precious metal-based materials, such as RuO2, IrO2 and their hybrids with other components, performed excellently as OER electrocatalysts, their high cost has limited practical applications. Consequently, earth-abundant metal components including Fe, Co, and Ni have been investigated as alternatives. In this work, the hybridization of Ni-containing species with conductive carbon-based materials was used to prevent aggregation of active species and improve electrochemical catalytic performance. A new hybrid material composed of NiO nanoparticles and N-doped carbon materials was prepared. The NiO particles with a narrow size distribution were well dispersed on the surface of carbon-based materials. The hybrid showed improved electrocatalytic performance for OER than single components of NiO and N-doped carbon materials.
The design and fabrication of catalysts with low-cost and high electrocatalytic activity for the oxygen evolution reaction (OER) have remained challenging because of the sluggish kinetics of this reaction. The key to the pursuit of efficient electrocatalysts is to design them with high surface area and more active sites. In this work, we have successfully synthesized a highly stable and active NiCo2S4 nanowire array on a Ni-foam substrate (NiCo2S4 NW/NF) via a two-step hydrothermal synthesis approach. This NiCo2S4 NW/NF exhibits overpotential as low as 275 mV, delivering a current density of 20 mA cm-2 (versus reversible hydrogen electrode) with a low Tafel slope of 89 mV dec-1 and superior long-term stability for 20 h in 1M KOH electrolyte. The outstanding performance is ascribed to the inherent activity of the binder-free deposited, vertically aligned nanowire structure, which provides a large number of electrochemically active surface sites, accelerating electron transfer, and simultaneously enhancing the diffusion of electrolyte.
Transition metal oxide is widely used as a water electrolysis catalyst to substitute for a noble metal catalyst such as IrO2 and RuO2. In this study, the sol-gel method is used to synthesize the CuxCo3-xO4 catalyst for the oxygen evolution reaction (OER),. The CuxCo3-xO4 is synthesized at various calcination temperatures from 250 ℃ to 400 ℃ for 4 h. The CuxCo3- xO4 synthesized at 300 ℃ has a perfect spinel structure without residues of the precursor and secondary phases, such as CuO. The particle size of CuxCo3-xO4 increases with an increase in calcination temperature. Amongst all the samples studied, CuxCo3- xO4, which is synthesized at 300?, has the highest activity for the OER. Its onset potential for the OER is 370 mV and the overpotential at 10 mA/cm2 is 438 mV. The tafel slope of CuxCo3-xO4 synthesized at 300 ℃ has a low value of 58 mV/dec. These results are mainly explained by the increase in the available active surface area of the CuxCo3-xO4 catalyst.
Microstructural evolution in the thickness direction of an oxygen free copper processed by accumulative rollbonding (ARB) is investigated by electron back scatter diffraction (EBSD) measurement. For the ARB, two copper alloy sheets 1 mm thick, 30 mm wide and 300 mm long are first degreased and wire-brushed for sound bonding. The sheets are then stacked and roll-bonded by about 50% reduction rolling without lubrication at an ambient temperature. The bonded sheet is then cut to the two pieces of the same dimensions and the same procedure was repeated on the sheets up to eight cycles. The specimen after 1 cycle showed inhomogeneous microstructure in the thickness direction so that the grains near the surface were finer than those near the center. This inhomogeneity decreased with an increasing number of ARB cycles, and the grain sizes of the specimens after 3 cycles were almost identical. In addition, the aspect ratio of the grains decreased with an increasing number of ARB cycles due to the subdivision of the grains by shear deformation. The fraction of grains with high angle grain boundaries also increased with continuing process of the ARB so that it was higher than that of the low angle grain boundaries in specimens after 3 cycles. A discontinuous dynamic recrystallization occurred partially in specimens after 5 cycles.