Facile synthesis of efficient Co3O4 nanostructures using the milky sap of Calotropis procera for oxygen evolution reactions and supercapacitor applications.

The preparation of Co3O4 nanostructures by a green method has been rapidly increasing owing to its promising aspects, such as facileness, atom economy, low cost, scale-up synthesis, environmental friendliness, and minimal use of hazardous chemicals. In this study, we report on the synthesis of Co3O4 nanostructures using the milky sap of Calotropis procera (CP) by a low-temperature aqueous chemical growth method. The milky sap of CP-mediated Co3O4 nanostructures were investigated for oxygen evolution reactions (OERs) and supercapacitor applications. The structure and shape characterizations were done by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) techniques. The prepared Co3O4 nanostructures showed a heterogeneous morphology consisting of nanoparticles and large micro clusters. A typical cubic phase and a spinel structure of Co3O4 nanostructures were also observed. The OER result was obtained at a low overpotential of 250 mV at 10 mA cm-2 and a low Tafel slope of 53 mV dec-1. In addition, the durability of 45 hours was also found at 20 mA cm-2. The newly prepared Co3O4 nanostructures using the milky sap of CP were also used to demonstrate a high specific capacitance of 700 F g-1 at a current density of 0.8 A g-1 and a power density of 30 W h kg-1. The enhanced electrochemical performance of Co3O4 nanostructures prepared using the milky sap of CP could be attributed to the surface oxygen vacancies, a relatively high amount of Co2+, the reduction in the optical band gap and the fast charge transfer rate. These surface, structural, and optical properties were induced by reducing, capping, and stabilizing agents from the milky sap of CP. The obtained results of OERs and supercapacitor applications strongly recommend the use of the milky sap of CP for the synthesis of diverse efficient nanostructured materials in a specific application, particularly in energy conversion and storage devices.

Transforming NiCo2O4 nanorods into nanoparticles using citrus lemon juice enhancing electrochemical properties for asymmetric supercapacitor and water oxidation.

Recently, the nanostructured nickel-cobalt bimetallic oxide (NiCo2O4) material with high electrochemical activity has received intensive attention. Beside this, the biomass assisted synthesis of NiCo2O4 is gaining popularity due to its advantageous features such as being low cost, simplicity, minimal use of toxic chemicals, and environment-friendly and ecofriendly nature. The electrochemical activity of spinel NiCo2O4 is associated with its mixed metal oxidation states. Therefore, much attention has been paid to the crystal quality, morphology and tunable surface chemistry of NiCo2O4 nanostructures. In this study, we have used citrus lemon juice consisting of a variety of chemical compounds having the properties of a stabilizing agent, capping agent and chelating agent. Moreover, the presence of several acidic chemical compounds in citrus lemon juice changed the pH of the growth solution and consequently we observed surface modified and structural changes that were found to be very effective for the development of energy conversion and energy storage systems. These naturally occurring compounds in citrus lemon juice played a dynamic role in transforming the nanorod morphology of NiCo2O4 into small and well-packed nanoparticles. Hence, the prepared NiCo2O4 nanostructures exhibited a new surface-oriented nanoparticle morphology, high concentration of defects on the surface (especially oxygen vacancies), sufficient ionic diffusion and reaction of electrolytic ions, enhanced electrical conductivity, and favorable reaction kinetics at the interface. The electrocatalytic properties of the NiCo2O4 nanostructures were studied in oxygen evolution reaction (OER) at a low overpotential of 250 mV for 10 mA cm-2, Tafel slope of 98 mV dec-1, and durability of 40 h. Moreover, an asymmetric supercapacitor was produced and the obtained results indicated a high specific capacitance of (Cs) of 1519.19 F g-1, and energy density of 33.08 W h kg-1 at 0.8 A g-1. The enhanced electrochemical performance could be attributed to the favorable structural changes, surface modification, and surface crystal facet exposure due to the use of citrus lemon juice. The proposed method of transformation of nanorod to nanoparticles could be used for the design of a new generation of efficient electrocatalyst materials for energy storage and conversion uses.

An Efficient Nickel Sulfide@NiO Nanocomposite Catalyst with High Density of Active Sites for the Hydrogen Evolution Reaction in Alkaline Media.

Efficient hydrogen evolution reaction (HER) catalysts based on the earth-abundant materials are highly vital to design practical and environmentally friendly water splitting devices. In this study, we present an optimized strategy for the development of active catalysts for hydrogen evolution reaction HER. The composite catalysts are prepared with the nanosurface of NiO for the deposition of NiS by hydrothermal method. In alkaline electrolyte, the NiS/NiO nanocomposite has shown excellent catalytic HER properties at the low onset potential and small Tafel slope of 72 mVdec-1. A current density of 10 mA/cm² is achieved by the nanocomposite obtained with 0.4 gram of NiO as nanosurface for the deposition of NiS (sample 4) at the cost of 429 mV versus RHE. The sample 4 carries more active sites that allow it to act as excellent HER catalyst. Based on this study, we conclude that increasing the nickel oxide content into composite sample facilitates the HER process. Additionally, a long term HER stability for 10 hours and good durability is also demonstrated by the sample 4. Our findings reveal that the optimization of nickel oxide content in the preparation of catalyst leads to the excellent HER activity for the design of practical water splitting devices and other related applications.

TiO2/ZnO Nanocomposite Material for Efficient Degradation of Methylene Blue.

In this research work, we have produced a composite material consisting titanium dioxide (TiO2) and zinc oxide (ZnO) nanostructures via precipitation method. Scanning electron microscopy (SEM) study has shown the mixture of nanostructures consisting nanorods and nano flower. Energy dispersive spectroscopy (EDS) study has confirmed the presence of Ti, Zn and O as main elements in the composite. X-ray diffraction (XRD) study has revealed that the successful presence of TiO2 and ZnO in the composite. The composite material exhibits small optical energy band gap which led to reduction of the charge recombination rate of electron-hole pairs. The band gap for the composite TiO2/ZnO samples namely 1, 2, 3 and 4 is 3.18, 3.00, 2.97 and 2.83 eV respectively. Small optical bandgap gives less relaxation time for the recombination of electron and hole pairs, thus favorable photodegradation is found. The degradation efficiency for the TiO2/ZnO samples for methylene blue in order of 55.03%, 75.7%, 85.14% and 90.08% is found for the samples 1, 2, 3 and 4 respectively. The proposed study of titanium dioxide addition into ZnO is facile and inexpensive for the development of efficient photocatalysts. This can be capitalized at large scale for the energy and.

Tin as an Effective Doping Agent into ZnO for the Improved Photodegradation of Rhodamine B.

We have fabricated ZnO nano rods by hydrothermal method and successively doped them with tin (Sn) using different concentrations of 25, 50, 75 and 100 mg of tin chloride. XRD of the fabricated structures showed that ZnO possess hexagonal wurtzite phase. Scanning electron microscopy (SEM) was used to explore the morphology and it shows nanorod like morphology for all samples and no considerable change in the structural features were found. The dimension of nanorod is 200 to 300 nm. The doped materials were then investigated for their photo catalytic degradation of environmental pollutant Rhodamine B. The performance of doped ZnO is compared with the pristine ZnO. Scanning electron microscopy (SEM) was used to explore the morphology and it shows nanorod like morphology for all samples and no considerable change in the structural features were found. The dimension of nanorod is 200 to 300 nm. XRD of the fabricated structures showed that ZnO possess hexagonal wurtzite phase. Photo catalytic activity of rhodamine B was investigated under UV light and a maximum degradation efficiency of 85% was obtained. The optical property reveals the reduction in band gap of upto 17.14% for 100 mg Sn doped ZnO. The degradation is followed by the pseudo order kinetics. The produced results are unique in terms of facile synthesis of Sn doped ZnO and excellent photo degradation efficiency, therefore these materials can be used for other environmental applications.

A Low Charge Transfer Resistance CuO Composite for Efficient Oxygen Evolution Reaction in Alkaline Media.

An efficient, simple, environment-friendly and inexpensive cupric oxide (CuO) electrocatalyst for oxygen evolution reaction (OER) is demonstrated. CuO is chemically deposited on the porous carbon material obtained from the dehydration of common sugar. The morphology of CuO on the porous carbon material is plate-like and monoclinic crystalline phase is confirmed by powder X-ray diffraction. The OER activity of CuO nanostructures is investigated in 1 M KOH aqueous solution. To date, the proposed electrocatalyst has the lowest possible potential of 1.49 V versus RHE (reversible hydrogen electrode) to achieve a current density of 20 mA/cm2 among the CuO based electrocatalysts and has Tafel slope of 115 mV dec-1. The electrocatalyst exhibits an excellent long-term stability for 6 hours along with significant durability. The enhanced catalytic active centers of CuO on the carbon material are due to the porous structure of carbon as well as strong coupling between CuO-C. The functionalization of metal oxides or other related nanostructured materials on porous carbon obtained from common sugar provides an opportunity for the development of efficient energy conversion and energy storage systems.

Chemically Coupled Cobalt Oxide Nanosheets Decorated onto the Surface of Multiwall Carbon Nanotubes for Favorable Oxygen Evolution Reaction.

Cobalt oxide has been widely investigated among potential transition metal oxides for the electrochemical energy conversion, storage, and water splitting. However, they have inherently low electronic conductivity and high corrosive nature in alkaline media. Herein, we propose a promising and facile approach to improve the conductivity and charge transport of cobalt oxide Co3O4 through chemical coupling with well-dispersed multiwall carbon nanotubes (MWCNTs) during hydrothermal treatment. The morphology of prepared composite material consisting of nanosheets which are anchored on the MWCNTs as confirmed by scanning electron microscopy (SEM). A cubic crystalline system is exhibited by the cobalt oxide as confirmed by the X-ray diffraction study. The Co, O, and C are the only elements present in the composite material. FTIR study has indicated the successful coupling of cobalt oxide with MWCNTs. The chemically coupled cobalt oxide onto the surface of MWCNTs composite is found highly active towards oxygen evolution reaction (OER) with a low onset potential 1.44 V versus RHE, low overpotential 262 mV at 10 mAcm-2 and small Tafel slope 81 mV dec-1. For continuous operation of 40 hours during durability test, no decay in activity was recorded. Electrochemical impedance study further revealed a low charge transfer resistance of 70.64 Ohms for the composite material during the electrochemical reaction and which strongly favored OER kinetics. This work provides a simple, low cost, and smartly designing electrocatalysts via hydrothermal reaction for the catalysis and energy storage applications.

An Efficient and Functional Fe3O4/Co3O4 Composite for Oxygen Evolution Reaction.

The design of efficient, stable, durable and noble metal free electro catalysts for oxygen evolution reaction (OER) are of immediate need, but very challenging task. In this study, iron induction into cobalt oxide (Co3O4) has resulted composite structure by wet chemical method. The iron impurity has brought an electronic disorder into Fe3O4/cobalt oxide composite thereby efficient oxygen evolution reaction is demonstrated. An addition of iron content into composite resulted the alternation of morphology from Nano rods to clusters of nanoparticles. The successive addition of iron into composite system reduced the onset potential of OER as compared to the pristine cobalt oxide. A Tafel slope of 80 mVdec-1 indicates the favorable oxygen evolution reaction kinetics on the sample 4. An over-potential of 370 mV is required to reach a 10 mAcm-2 current density which is acceptable for a nonprecious catalyst. The catalyst is highly durable and stable for 30 hours. Electrochemical impedance spectroscopy further provided a deeper insight on charge transfer resistance and sample 4 has low charge transfer resistance that supported the OER polarization curves. The sample 4 has more electrochemical active surface area of 393.5 cm². These obtained results are exciting and highlighting the importance of composite structure and leave a huge space for the future investigations on composite materials for energy related applications.

Facile doping of nickel into Co3O4 nanostructures to make them efficient for catalyzing the oxygen evolution reaction.

Designing a facile and low-cost methodology to fabricate earth-abundant catalysts is very much needed for a wide range of applications. Herein, a simple and straightforward approach was developed to tune the electronic properties of cobalt oxide nanostructures by doping them with nickel and then using them to catalyze the oxygen evolution reaction (OER) in an aqueous solution of 1.0 M KOH. The addition of a nickel impurity improved the conductivity of the cobalt oxide, and further increased its activity towards the OER. Analytical techniques such as scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and powder X-ray diffraction (XRD) were used to investigate, respectively, the morphology, composition and crystalline structure of the materials used. The nickel-doped cobalt oxide material showed randomly oriented nanowires and a high density of nanoparticles, exhibited the cubic phase, and contained cobalt, nickel and oxygen as its main elements. The nickel-doped cobalt oxide also yielded a Tafel slope of 82 mV dec-1 and required an overpotential of 300 mV to reach a current density of 10 mA cm-2. As an OER catalyst, it was shown to be durable for 40 h. Electrochemical impedance spectroscopy (EIS) analysis showed a low charge-transfer resistance of 177.5 ohms for the nickel-doped cobalt oxide, which provided a further example of its excellent OER performance. These results taken together indicated that nickel doping of cobalt oxide can be accomplished via a facile approach and that the product of this doping can be used for energy and environmental applications.

Efficient tri-metallic oxides NiCo2O4/CuO for the oxygen evolution reaction.

In this study, a simple approach was used to produce nonprecious, earth abundant, stable and environmentally friendly NiCo2O4/CuO composites for the oxygen evolution reaction (OER) in alkaline media. The nanocomposites were prepared by a low temperature aqueous chemical growth method. The morphology of the nanostructures was changed from nanowires to porous structures with the addition of CuO. The NiCo2O4/CuO composite was loaded onto a glassy carbon electrode by the drop casting method. The addition of CuO into NiCo2O4 led to reduction in the onset potential of the OER. Among the composites, 0.5 grams of CuO anchored with NiCo2O4 (sample 2) demonstrated a low onset potential of 1.46 V vs. a reversible hydrogen electrode (RHE). A current density of 10 mA cm-2 was achieved at an over-potential of 230 mV and sample 2 was found to be durable for 35 hours in alkaline media. Electrochemical impedance spectroscopy (EIS) indicated a small charge transfer resistance of 77.46 ohms for sample 2, which further strengthened the OER polarization curves and indicates the favorable OER kinetics. All of the obtained results could encourage the application of sample 2 in water splitting batteries and other energy related applications.