Co3O4 Nanostructures Research Articles

Sensitive detection of persulfate by a novel self-powered electrochemical sensor with carbon cloth electrodes modified with tin-doped cobalt tetroxide.

The accurate and rapid detection of persulfate concentration is important for environmental decontamination and human health protection. In this work, a novel self-powered electrochemical sensor for the sensitive monitoring of persulfate was developed, which utilized cobalt tetroxide (Co3O4@CC) or tin-doped cobalt tetroxide (SnxCo3-xO4@CC) cathode as the sensing element and anode with electrogenic microorganisms as the power supplier. The Co3O4@CC and SnxCo3-xO4@CC electrodes were fabricated by in situ growing nanostructured Co3O4 or SnxCo3-xO4 catalysts on carbon cloth. Electrochemical tests revealed that these electrodes exhibited excellent catalytic reduction performance toward persulfate because of the synergistic catalysis by Co3O4 and electrode electrons, well-exposed Co2+/Co3+ catalytic sites, and high electron transfer efficiency. Tin doping could enhance the catalytic persulfate reduction by improving the conductivity and electron transfer of the Co3O4 catalyst. The electrode prepared at a hydrothermal temperature of 90°C and a tin dosage of 0.286g·cm-2 achieved the highest persulfate reduction activity under pH 7. The sensing properties of the self-powered sensors toward persulfate were explored in detail. Results showed that under the optimal external load of 300 Ω, the proposed sensor could display a broad detection range of 0 to 1500μmol L-1 K2S2O8 with sensitivities of 1.13 and 0.12 μA μmol-1 L, a detection limit of 1.11μmol L-1 (S/N = 3), and a fast response time within 30s. The sensors also presented satisfactory reproducibility and selectivity during the detection of persulfate. The proposed sensor will provide a new approach for sensitive, on-site, and real-time monitoring of persulfate for a wide range of applications.

Co3O4 nanoparticles synthesized with rotten-grape extract for use in supercapacitors and oxygen evolution devices

Phytochemicals in grape fruit juice have never been considered as potential sources of surface modification, shape modification, and energy storage. In our study, we demonstrate the hydrothermal synthesis of Co3O4 nanostructures from grape fruit extracts. X-ray diffraction analysis revealed that Co3O4 nanostructures exhibit a cubic phase, while Fourier transform infrared spectroscopy identified several functional groups. An analysis of Co3O4 nanostructures using a scanning electron microscope revealed that uniformly distributed nanoparticles of Co3O4 were trapped in the carbon content of the spices during calcination. UV–visible spectrometer analysis of Co3O4 nanostructures reveals a wide range of optical bands. It was found that one mL of grape fruit juice provided the lowest optical band gap of 2.51 eV for Co3O4 nanostructures. Nanostructures of Co3O4 were studied under alkaline conditions for use in supercapacitors and oxygen evolution reactions. An aqueous solution containing 1 mL of assisted Co3O4 nanostructures exhibited an overpotential of 290 mV at a current density of 10 mA cm−2 in 1 M KOH. In addition, they showed a Tafel slope of 80 mV dec−1. When dissolved in 3 M KOH electrolyte, grape fruit juice assisted Co3O4 nanostructures showed a specific capacitance of 867 F/g at 1.5 A/g in 3 M KOH aqueous solution. A specific capacitance retention percentage of about 101.1 % was achieved after 40000 galvanic charge-discharge cycles. It has been shown that the total photochemistry of biomass waste can be tuned and enhanced to enhance the functional properties of nanostructures derived from rotten grape fruit extract in order to develop functional materials with high performance for a wide range of applications.

Investigating the photocatalytic properties of ZnO-Co3O4 nanocomposites synthesized via solution combustion method

This study investigated the photocatalytic degradation of CR, MB, and RhB dyes using Co3O4 nanostructures and ZnO-Co3O4 nanocomposites synthesized via solution combustion. Co3O4 nanostructures had an average size of 14.56 nm and a band gap of 1.66 eV, while ZnO-Co3O4 nanocomposites had an average size of 11.12 nm and a band gap of 1.69 eV. FESEM analysis showed porous structures for Co3O4 and agglomerated nanoparticles for ZnO-Co3O4. Under UV irradiation, ZnO-Co3O4 nanocomposites showed superior performance, achieving 83.46 %, 99.78 %, and 98.65 % degradation for CR, MB, and RhB dyes in 100, 100, and 60 min, respectively. The Langmuir–Hinshelwood model revealed significantly higher rate constants for ZnO-Co3O4 nanocomposites compared to Co3O4 nanostructures, with improvements of 3.274, 2.042, and 4.917 times for CR, MB, and RhB dyes. These findings highlight the potential of these nanocomposites as effective photocatalysts for environmental remediation.

Earth-Abundant Metal Oxides as Oxygen Evolution Electrocatalysts in 1 M H2SO4

Water splitting is a very hot research topic as a preferred source for green hydrogen, as a key vector to facilitate a transition into an environmentally friendly and sustainable energy economy in the mid-term. But it is still far from being economically competitive with respect to current hydrogen production technologies based on fossil fuels. One of the major economic hurdles to reduce electrolysis costs is the lack of low-cost catalysts for hydrogen evolution and, more importantly, for oxygen evolution. The water oxidation process is considered the main bottleneck in the advancement of water splitting devices, since it is the rate limiting process, and the main cause of poor long-term performance.Most recent advances in the field of water oxidation catalysis are based on transition metal oxides, operating exclusively in alkaline electrolysis conditions. Unfortunately, these excellent oxygen evolution catalysts in basic pH ( > 13) rapidly lose their activity when the pH is lowered, and are far away from the performance exhibited by noble metals in acid solution. McCrory et al. established in 2013 1a benchmarking protocol to identify the potential of new OER electrocatalysts (and extended in 2015 2 to HER) comparing the initial activity and stability of the materials as a function of pH and showed how no other known catalysts at that time came close to the performance of IrOx-based materials.A simple processing technique using a partially hydrophobic binder has been proved to stabilize Co oxide, resulting in electrodes able to reach high current densities (> 10 mA cm-2) at competitive overpotentials and with long term stability for acidic OER catalysis3. Following this strategy, we have been able to conduct an extensive survey of the activity and stability of monometallic, binary and ternary earth-abundant transition metal oxides during electrocatalytic OER in 1 M H2SO4. Our results confirm the general validity of the strategy in using a partially hydrophobic electrode to confer high stability to common metal oxides under these harsh conditions.[1] C.C.L. McCrory, S. Jung, J.C. Peters, T.F. Jaramillo, Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction, J. Am. Chem. Soc. 135 (2013) 16977–16987.[2] C.C.L. McCrory, S. Jung, I.M. Ferrer, S.M. Chatman, J.C. Peters, T.F. Jaramillo, Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices, J. Am. Chem. Soc. 137 (2015) 4347–4357.[3] J. Yu, F.A. Garcés-Pineda, J. González-Cobos, M. Peña-Díaz, C. Rogero, S. Giménez, M.C. Spadaro, J. Arbiol, S. Barja, J.R. Galán-Mascarós, Sustainable oxygen evolution electrocatalysis in aqueous 1 M H2SO4 with earth abundant nanostructured Co3O4, Nat. Commun. 13 (2022) 4341. Figure 1

Facet-Dependent Evolution of Active Components on Spinel Co3O4 for Electrochemical Ammonia Synthesis.

Spinel cobalt oxides (Co3O4) have emerged as a promising class of catalysts for the electrochemical nitrate reduction reaction (eNO3RR) to ammonia, offering advantages such as low cost, high activity, and selectivity. However, the specific role of crystallographic facets in determining the catalysts' performance remains elusive, impeding the development of efficient catalysts. In this study, we have synthesized various Co3O4 nanostructures with exposed facets of {100}, {111}, {110}, and {112}, aiming to investigate the dependence of the eNO3RR activity on the crystallographic facets. Among the catalysts tested, Co3O4 {111} shows the best performance, achieving an ammonia Faradaic efficiency of 99.1 ± 1.8% with a yield rate of 35.2 ± 0.6 mg h-1 cm-2 at -0.6 V vs RHE. Experimental and theoretical results reveal a transformation process in which the active phases evolve from Co3O4 to Co3O4-x with oxygen vacancy (Ov), followed by a Co3O4-x-Ov/Co(OH)2 hybrid, and finally Co(OH)2. This process is observed for all facets, but the formation of Ov and Co(OH)2 is the most rapid on the (111) surface. The presence of Ov significantly reduces the free energy of the *NH2 intermediate formation from 1.81 to -0.53 eV, and plentiful active sites on the densely reconstructed Co(OH)2 make Co3O4 {111} an ideal catalyst for ammonia synthesis via eNO3RR. This work provides insights into the understanding of the realistic active components, offers a strategy for developing highly efficient Co-based spinel catalysts for ammonia synthesis through tuning the exposed facets, and helps further advance the design and optimization of catalysts in the field of eNO3RR.

Scalable Cathodic H2O2 Electrosynthesis using Cobalt-Coordinated Nanocellulose Electrocatalyst.

Converting hierarchical biomass structure into cutting-edge architecture of electrocatalysts can effectively relieve the extreme dependency of nonrenewable fossil-fuel-resources typically suffering from low cost-effectiveness, scarce supplies, and adverse environmental impacts. A cost-effective cobalt-coordinated nanocellulose (CNF) strategy is reported for realizing a high-performance 2e-ORR electrocatalysts through molecular engineering of hybrid ZIFs-CNF architecture. By a coordination and pyrolysis process, it generates substantial oxygen-capturing active sites within the typically oxygen-insulating cellulose, promoting O2 mass and electron transfer efficiency along the nanostructured Co3O4 anchored with CNF-based biochar. The Co-CNF electrocatalyst exhibits an exceptional H2O2 electrosynthesis efficiency of ≈510.58mgL-1cm-2h-1 with an exceptional superiority over the existing biochar-, or fossil-fuel-derived electrocatalysts. The combination of the electrocatalysts with stainless steel mesh serving as a dual cathode can strongly decompose regular organic pollutants (up to 99.43% removal efficiency by 30min), showing to be a desirable approach for clean environmental remediation with sustainability, ecological safety, and high-performance.

Performance tweaking of Co3O4 UV radiation detector via zirconium dopant microstructural and photo-electronic engineering

Incorporation of dopant impurities in semiconducting metal oxide nanostructures has been presumed to increase the pace at which photo-induced holes and electrons separate due to possible bandgap engineering and oxygen vacancy modulations. In this study, we have adopted an electrodeposition technique using a three-electrode configuration for the preparation of Co3O4 thin film samples and investigated the effect of Zr as a dopant ion on the UV radiation sensing performance of nanostructured Co3O4 host material via energy band engineering and microstructural modulation. Consistency in optical energy band gap measurements of the deposited Zr-doped Co3O4 (Zr@Co3O4) was unveiled with the aid of two models: Tauc’s and absorption spectrum fitting (ASF) methods. Ag/Zr@Co3O4/ITO/glass UV radiation detector was fabricated and a sample with 3 % Zr-dopant content demonstrated high UV-365 nm detector performance: detectivity, 1.2 ×1011 Jones, and responsivity, 1818 mA W−1, with high cycling stability, attributable to the host's dopant microstructural tailoring, and the enhancement in its electronic charge carrier number and their scattering potentials within the host's band structure, thanks to the synergistic impacts of dopant ion incorporation and UV irradiation.

Exploring the effect of morphology on electrochemical performance of nickel and cobalt metal-organic frameworks and their derivatives for supercapacitor and hydrogen evolution

This study explores the novel approach of investigating the use of binder-free nickel and cobalt metal-organic frameworks and their metal oxide derivatives in 1D, 2D, and 3D morphologies on Ni foam for applications in supercapacitors and hydrogen evolution. This research work involves changing parameters like precursor concentration, organic linkers, and reaction time, leading to the formation of stable one-, two-, and three-dimensional NiO and Co3O4 nanostructures. The morphologies of pristine MOFs and their corresponding oxides were comprehensively verified through FESEM analysis. Significantly, the materials with two-dimensional growth exhibited superior electrochemical performance in supercapacitors and good electrocatalytic performance in hydrogen evolution reaction when compared to their one-dimensional and three-dimensional counterparts. Among them, 2D NiO demonstrated exceptional performance as a supercapacitor electrode, with a specific capacity of 688.13 C g−1 (1376.26 F g−1) at 1 A g−1, surpassing 1D and 3D NiO nanostructures. It also demonstrated good stability by retaining 93.1 % of its initial capacity after 5000 cycles at 10 A g−1. The assembled asymmetric supercapacitor (ASC) achieved a high energy density of 65.27 Wh kg−1 at 375 W kg−1, maintaining 33.18 Wh kg−1 even at 7500 W kg−1. It also maintained 87.8 % retention of its initial capacity up to 5000 cycles at 10 A g−1. Furthermore, when tested for HER, all oxides exhibited better performances with specifically 2D NiO exhibiting good catalytic performance, reaching 10 mA cm−2 at a low overpotential of 129 mV (vs. RHE) and displaying remarkable stability over 24 h. This study upholds the superiority of two-dimensional sheet-like structures with interconnected network of nanoparticles in electrochemical and electrocatalytic performance compared to one-dimensional rod-like and three-dimensional pyramid-like structures.

Investigation and Comparative Studies on Charge Storage Performance in Nanostructured RuO2, NiO and Co3O4 Nanoparticles for High Dense Energy Storage

Investigation and Comparative Studies on Charge Storage Performance in Nanostructured RuO2, NiO and Co3O4 Nanoparticles for High Dense Energy Storage

Rational Construction of Pt Incorporated Co3O4 as High-Performance Electrocatalyst for Hydrogen Evolution Reaction.

Electrocatalysts in alkaline electrocatalytic water splitting are required to efficiently produce hydrogen while posing a challenge to show excellent performances. Herein, we have successfully synthesized platinum nanoparticles incorporated in a Co3O4 nanostructure (denoted as Pt-Co3O4) that show superior HER activity and stability in alkaline solutions (the overpotentials of 37 mV to reach 10 mA cm-2). The outstanding electrocatalytic activity originates from synergistic effects between Pt and Co3O4 and increased electron conduction. Theoretical calculations show a significant decrease in the ΔGH* of Co active sites and a remarkable increase in electron transport. Our work puts forward a special and simple synthesized way of adjusting the H* adsorption energy of an inert site for application in HER.

A Novel Approach for Efficient Water Oxidation and Supercapacitor Applications Based on Morphologically Transformed, Surface Rich Oxygen Vacancies of Co3o4 Nanostructures Co-Synthesized with Potato Starch Peel Extract

A Novel Approach for Efficient Water Oxidation and Supercapacitor Applications Based on Morphologically Transformed, Surface Rich Oxygen Vacancies of Co3o4 Nanostructures Co-Synthesized with Potato Starch Peel Extract

Chemical vapor deposition-grown single-layer graphene-supported nanostructured Co3O4 composite as binder-free electrode for asymmetric supercapacitor and electrochemical detection of caffeic acid

In this study, we developed a monolayer graphene/nanostructured cobalt oxide (MLG/Co3O4) composite for asymmetric supercapacitor and electrochemical sensor applications. The MLG was grown by chemical vapor deposition process and the Co3O4 nanostructures were electrodeposited on the MLG surface. Scanning electron microscopy proved that there were flower-like nanostructured Co3O4 densely electrodeposited on the MLG surface. At a current density of 3 mA cm−2, the MLG/Co3O4 composite produced an areal capacitance of 3.73 F cm−2. After 10,000 cycles, the composite electrode still had 93.6 % of its initial capacitance at 5 mA cm−2. The asymmetric system displayed an areal capacitance of 929 mF cm−2 at 4 mA cm−2 with good cycle stability. The asymmetric electrode produced a specific energy of 51 μWh cm−2 and a specific power of 11.1 mW cm−2. Cyclic voltammetric measurements demonstrated that the composite showed redox peaks at 0.48 eV and 0.09 eV toward the determination of CA. With a sensitivity of 0.13 µA/µM/cm2 and a limit of detection of 0.009 µM, the composite showed CA concentrations, ranging from 0.5 to 480 M. The composite displayed excellent selectivity and the current produced for the interfering compounds was exceedingly low. Using the composite electrode, the spiked CA in red wine and green tea samples recovered remarkably effectively.

Constructing a potential electrocatalyst: highly multi-porous Co3O4 nanostructures to enhance electrocatalytic oxygen evolution reactions

Constructing a potential electrocatalyst: highly multi-porous Co3O4 nanostructures to enhance electrocatalytic oxygen evolution reactions

MOF-based Ag NPs/Co3O4 nanozyme for colorimetric detection of thiophanate-methyl based on analyte-enhanced sensing mechanism.

Silver nanoparticles supported on metal-organic framework (ZIF-67)-derived Co3O4 nanostructures (Ag NPs/Co3O4) were synthesized via a facile in situ reduction strategy. The resulting materials exhibited pH-switchable peroxidase/catalase-like catalytic activity. Ag NP doping greatly enhanced the catalytic activity of Ag NPs/Co3O4 towards 3,3',5,5'-tetramethylbenzidine (TMB) oxidation and H2O2 decomposition which were 59 times (A652 of oxTMB) and 3 times (A240 of H2O2) higher than that of ZIF-67, respectively. Excitingly, thiophanate-methyl (TM) further enhanced the peroxidase-like activity of Ag NPs/Co3O4 nanozyme due to the formation of Ag(I) species in TM-Ag NPs/Co3O4 and generation of more radicals resulting from strong interaction between Ag NPs and TM. The TM-Ag NPs/Co3O4 nanozyme exhibited lower Km and higher Vmax values towards H2O2 when compared with Ag NPs/Co3O4 nanozyme. A simple, bioelement-free colorimetric TM detection method based on Ag NPs/Co3O4 nanozyme via analyte-enhanced sensing strategy was successfully established with high sensitivity and selectivity. Our study demonstrated that hybrid noble metal NPs/MOF-based nanozyme can be a class of promising artificial nanozyme in environmental and food safety applications.

Three-Dimensional Network of Highly Uniform Cobalt Oxide Microspheres/MXene Composite as a High-Performance Electrocatalyst in Hydrogen Evolution Reaction.

Due to its affordable cost, excellent redox capability, and relatively effective resistance to corrosion in alkaline environments, spinel Co3O4 demonstrates potential as a viable alternative to noble-metal-based electrocatalysts. Nevertheless, these materials continue to exhibit drawbacks, such as limited active surface area and inadequate intrinsic conductivity. Researchers have been trying to increase the electrical conductivity of Co3O4 nanostructures by integrating them with various conductive substrates due to the low conductivity of pristine Co3O4. In this study, uniform cobalt glycerate solid spheres are first synthesized as the precursor and subsequently transformed into cobalt oxide microspheres by a simple annealing procedure. Co3O4 grown on the surface of Ti3C2Tx-MXene nanosheets (Co3O4/MXene) was successfully synthesized through electrostatic attraction. In order to create a positively charged surface, the Co3O4 microspheres were treated with aminopropyltriethoxysilane. The Co3O4/MXene exhibited a low overpotential of 118 mV at 10 mA cm-2 and a Tafel slope of 113 mV dec-1 for the hydrogen evolution reaction, which is much lower than the pristine Co3O4 at 232 and 195.3 mV dec-1.

Analysis of CNT and rGO Mediation for an Efficient Super-Capacitive Response in Cr-Doped Co3O4 Based Composites

The synthesis of novel and high capacitance electrode materials has attracted much attention over the last few decades to meet the needs of electrode materials in supercapacitors. Cobalt oxide, one of several vanadium oxides, has recently gained popularity due to its unique layered structure, phase transition, and applications in supercapacitors. Here, we present structural, morphological, and electrochemical analysis of Cr-doped Co3O4 nanostructures and their carbon nanotubes/reduced graphene oxide (CNT/rGO) based composites. Hydrothermal and solvothermal routes are followed to prepare the samples. The active material is developed via a polymer-based binder and is used as the electrode in a three-electrode electrochemical system. X-ray diffraction confirms the spinel-type cubic crystal structure, while the stoichiometric elemental contents are verified via an energy dispersive X-ray spectroscopy. Well-shaped layered growth of the nanocomposites is revealed by field emission scanning electron microscopy. The electrochemical analysis is performed using a 2 M KOH electrolyte solution and a three-electrode electrochemical setup. The pure and Cr-doped nanocomposite samples reveal a pseudo capacitive behavior in all samples. The systematic capacitive and resistive response of the samples has also been presented in this report. The aforementioned attributes make the synthesized specimen a potential candidate for an electrode material.

Preparation and morphology controlling of Co3O4 nanostructures and their gas-sensing properties

Preparation and morphology controlling of Co3O4 nanostructures and their gas-sensing properties

Highly-enhanced toluene gas-sensing behavior of high-valent metal-cations doped Co3O4 nanostructures derived from ZIF-67 MOF

In this paper, the different valent metal-cations (Zn2+, In3+ and Zr4+) doped porous Co3O4 nanostructures were synthesized through the pyrolysis of ZIF-67 metal–organic framework (MOF). The influence of the different valence and doping content of metal-cations on the morphology, microstructures and gas-sensing performance of Co3O4 sensors is discussed in detail. The Zr-doped Co3O4 nanostructures present the higher specific surface area for the smaller average grain size, and the toluene gas-sensing performance of Co3O4 nanostructures is significantly improved with the high-valent Zr-doping. The high valence Zr-doping greatly improves the toluene gas-sensing properties, which Co2.717Zr0.189O4 sensor exhibits the highest response value of 94.58 to 100 ppm toluene gas (3.8-fold of Co3O4 sensor). The donor Zr-doping to p-type Co3O4 nanostructures optimizes the hole distribution and further affects Fermi level. Combining with the more oxygen adsorption from the high specific surface area, the resistance in air greatly decreases and resistance in toluene gas increases.

Co3O4 Nanostructured Sensor for Electrochemical Detection of H2O2 as a Stress Biomarker in Barley: Fe3O4 Nanoparticles-Mediated Enhancement of Salt Stress Tolerance.

This research investigates the enhancement of barley's resistance to salt stress by integrating nanoparticles and employing a nanostructured Co3O4 sensor for the electrochemical detection of hydrogen peroxide (H2O2), a crucial indicator of oxidative stress. The novel sensor, featuring petal-shaped Co3O4 nanostructures, exhibits remarkable precision and sensitivity to H2O2 in buffer solution, showcasing notable efficacy in complex analytes like plant juice. The research establishes that the introduction of Fe3O4 nanoparticles significantly improves barley's ability to withstand salt stress, leading to a reduction in detected H2O2 concentrations, alongside positive impacts on morphological parameters and photosynthesis rates. The developed sensor promises to provide real-time monitoring of barley stress responses, providing valuable information on increasing tolerance to crop stressors.

Mo-doped porous Co3O4 nanoflakes as an electrode with the enhanced capacitive contribution for asymmetric supercapacitor application

Cobalt oxide (Co3O4) electrode materials have tremendous properties for supercapacitors, such as being environmentally friendly, having a high surface area, being low cost, and having high theoretical specific capacitance (3560 Fg−1). However, its poor electronic conductivity restricts the performance of the practical application. Doping transition metal ions into the host materials is an effective method to improve conductivity and enhance storage capacity. In this research work, we studied Mo-doped Co3O4 nanostructure electrodes synthesized using the electrodeposition technique. The integrated material samples were characterized by XRD, SEM with EDAX, XPS, FTIR, Raman spectra, UV–visible, and BET for their structure, morphology, composition, optical, and surface area properties. The 2 mM Mo-doped Co3O4 electrode exhibits excellent electrochemical pseudocapacitive properties. The optimized Mo2-doped Co3O4 shows a maximum specific capacitance of 1674 Fg−1 at 10 mA cm−2 current density in 1 M KOH electrolyte solution. Finally, the asymmetrical hybrid supercapacitor device (AsHScD) Mo2-Co3O4//rGO) demonstrates the highest power density of 159.0 KWKg−1 and maximum energy density of 13.80 WhKg−1 with a long-term stability of 95 % up to 2000 cycles. The Mo2-Co3O4 electrode is a promising candidate material for a charge-storage hybrid supercapacitor in an aqueous 1 M KOH electrolyte.