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1.
The influence of lithium oxide-doping on the thermal stability of Co3O4 was studied using DTA, TG, DTG and X-ray diffraction techniques. Pure and doped cobaltic oxide specimens were prepared by thermal decomposition of pure basic cobalt carbonate and the basic carbonate mixed with different proportions of LiOH, in air, at different temperatures between 500 and 1100°C.Pure Co3O4 was found to start partial decomposition when heated in air at 830°C yielding the CoO phase. The complete decomposition was effected by heating at 1000°C.Doping of Co3O4 with different proportions of Li2O was found to much increase its thermal stability. The temperatures at which the doped oxide samples started to undergo decomposition were increased to 865, 910 and 1050°C for 0.375, 0.75 and 3% Li2O-doped solids, respectively. The DTA revealed that the 1.5% Li2O-doped cobaltic oxide did not undergo any thermal decomposition till 1080°C. The X-ray investigation showed that the prolonged heating of 1.5 and 3% Li2O-doped solids at 1100°C for 36 h effected only a partial decomposition of Co3O4 into CoO. Heating of these solids at temperatures varying between 900 and 1100°C led also to the formation of a new lithium oxide cobaltic oxide phase, the composition of which has not yet been identified.The role of Li2O in increasing the thermal stability of Co3O4 was attributed to the substitution of some of its cobalt ions by Li+ ions, according to Verwey and De Boer's mechanism, leading to the transformation of some of the Co2+ into Co3+ ions thus increasing the oxidation state of the cobaltic oxide lattice.  相似文献   

2.
Layered LiNi0.4Co0.2Mn0.4O2, Li[Li0.182Ni0.182Co0.091Mn0.545]O2, Li[Li1/3Mn2/3]O2 powder materials were prepared by rheological phase method. XRD characterization shows that these samples all have analogous structure to LiCoO2. Li[Li0.182Ni0.182Co0.091Mn0.545]O2 can be considered to be the solid solution of LiNi0.4Co0.2Mn0.4O2 and Li[Li1/3Mn2/3]O2. Detailed information from XRD, ex situ XPS measurement and electrochemical analysis of these three materials reveals the origin of the irreversible plateau (4.5 V) of Li[Li0.182Ni0.182Co0.091Mn0.545]O2 electrode. The irreversible oxidation reaction occurred in the first charging above 4.5 V is ascribed to the contribution of Li[Li1/3Mn2/3]O2 component, which maybe extract Li+ from the transition layer in Li[Li1/3Mn2/3]O2 or Li[Li0.182Ni0.182Co0.091Mn0.545]O2 through oxygen release. This step also activates Mn4+ of Li[Li1/3Mn2/3]O2 or Li[Li0.182Ni0.182Co0.091Mn0.545]O2, it can be reversibly reduced/oxidized between Mn4+ and Mn3+ in the subsequent cycles.  相似文献   

3.
A high‐sensitivity carcinoembryonic antigen immunosensor was successfully prepared via a one‐step hydrothermal method, wherein nitrogen‐doped graphene oxide (Nr GO) loaded Ag and Co3O4 nanomaterials were synthesized using ammonia as the nitrogen source. Doping nitrogen atoms into the graphene structure forms a new type of N‐type semiconductor with an increased number of graphene layers and more active sites for bonding with chemicals, thereby providing excellent in biocompatibility and good electrical conductivity. The electrical signal of the sensor is further amplified due to the good catalytic effect of Co3O4 and Ag NPs on H2O2. The signal probe requires neither pretreatment nor acid treatment, and can be easy to loaded with metal‐immobilized antibodies, which greatly simplifies the detection step not shorten the detection time. The sensor has good sensitivity to detecting carcinoembryonic antigen (CEA) and can easily operate, and requires mild reaction conditions. Under optimal experimental conditions, the linear range of the sensor is 0.001–200 ng ? mL?1, the detection limit is 0.18 pg ? mL?1, and the linear correlation coefficient is 0.991, which can be used for CEA determination of the actual sample.  相似文献   

4.
Formation constants of mixed ligand complexes of Cu2+, Zn2+, Ni2+, Co2+, and Mn2+,with cyadine-5′-monophosphoric acid (CMP) and various primary ligands such as 1,10-phenanthroline(phen), glycylglycine(glygly) and salicylic acid (sal) have been determined in aqueous solution at 35°C and 0.1 M (KNO3) by potentiomeric measurements. The acid dissociation constants of all the above mentioned ligands together with their 1 : 1 binary metal complex formation constants were also measured at 35°C. In general all the 1 : 1 binary complexes follow the Irving-Williams order of stability. Further the binary metal complexes of primary ligands are more stable than their ternary complexes with CMP. For ternary complexes, Δ(log K) values seem to change from positive to highly negative as the coordinating atoms of the primary ligands were varied from N,N to N,O? to O?O?. The higher stability of ternary complexes involving phen is due to its Π-bonding interaction with the above metal ions and the relative decrease in the stability of other ternary systems is due to the coulombic repulsion of donor oxygen atoms of primary and secondary ligands. Thus for ternary complexes the stabilities follow a decreasing order of M-phen-CMP > M-glygly-CMP > M-sal-CMP.  相似文献   

5.
Substitution of Li+ into Co3O4 and ZnCo2O4 gives rise to the solid solution series LixM1?xCo2O4 (M = Co2+ or Zn2+) having the spinel structure upto x = 0.4. X-Ray diffraction intensities show that the spinel solid solutions are likely to have the following cation distributions: (Co2+)t[Li+xCo3+2?3xCo4+2x]0O4 and (Zn2+1?xCo2+x)t[Li+xCo3+2?3xCo4+2x]0O4. Electrical resistivity and Seebeck coefficient data indicate that the electron transport in these systems occurs by a small-polaron hopping mechanism.  相似文献   

6.
Co3O4, which is of mixed valences Co2+ and Co3+, has been extensively investigated as an efficient electrocatalyst for the oxygen evolution reaction (OER). The proper control of Co2+/Co3+ ratio in Co3O4 could lead to modifications on its electronic and thus catalytic properties. Herein, we designed an efficient Co3O4‐based OER electrocatalyst by a plasma‐engraving strategy, which not only produced higher surface area, but also generated oxygen vacancies on Co3O4 surface with more Co2+ formed. The increased surface area ensures the Co3O4 has more sites for OER, and generated oxygen vacancies on Co3O4 surface improve the electronic conductivity and create more active defects for OER. Compared to pristine Co3O4, the engraved Co3O4 exhibits a much higher current density and a lower onset potential. The specific activity of the plasma‐engraved Co3O4 nanosheets (0.055 mA cm?2BET at 1.6 V) is 10 times higher than that of pristine Co3O4, which is contributed by the surface oxygen vacancies.  相似文献   

7.
This work reports the synthesis of various carbon (Vulcan XC-72 R) supported metal oxide nanostructures, such as Mn2O3, Co3O4 and Mn2O3−Co3O4 as heterogeneous Fenton-like catalysts for the degradation of organic dye pollutants, namely Rhodamine B (RB) and Congo Red (CR) in wastewater. The activity results showed that the bimetallic Mn2O3−Co3O4/C catalyst exhibits much higher activity than the monometallic Mn2O3/C and Co3O4/C catalysts for the degradation of both RB and CR pollutants, due to the synergistic properties induced by the Mn−Co and/or Mn (Co)−support interactions. The degradation efficiency of RB and CR was considerably increased with an increase of reaction temperature from 25 to 45°C. Importantly, the bimetallic Mn2O3−Co3O4/C catalyst could maintain its catalytic activity up to five successive cycles, revealing its catalytic durability for wastewater purification. The structure–activity correlations demonstrated a probable mechanism for the degradation of organic dye pollutants in wastewater, involving •OH radical as well as Mn2+/Mn3+ or Co2+/Co3+ redox couple of the Mn2O3−Co3O4/C catalyst.  相似文献   

8.
Low temperature synthesis and electrochemical properties of partially substituted lithium manganese oxides are reported. We demonstrate various metallic cations (Cu2+, Ni2+, Fe3+, Co3+) can be incorporated in the 3 V layered cathodic material Li0.45MnO2.1. New compounds Li0.45Mn0.88Fe0.12O2.1, Li0.45Mn0.84Ni0.16O2.05, Li0.45Mn0.79Cu0.21O2.3, Li0.45Mn0.85Co0.15O2.3 are prepared. These 3 V cathode materials are characterized by the same shape of discharge-charge profiles but different values of the specific capacity, between 90 mAh g−1 and 180 mAh g−1. The best results in terms of capacity and cycle life are obtained with the selected content of 0.15 Co per mole of oxide, as the optimum composition. The high kinetics of Li+ transport in Li0.45Mn0.85Co0.15O2.3 compared to that in the Co-free material is consistent with a substitution of Mn(III) by Co(III) in MnO2 sheets.  相似文献   

9.
Layered, lithium-rich Li[Li0.2Co0.3Mn0.5]O2 cathode material is synthesized by reactions under autogenic pressure at elevated temperature (RAPET) method, and its electrochemical behavior is studied in 2?M Li2SO4 aqueous solution and compared with that in a non-aqueous electrolyte. In cyclic voltammetry (CV), Li[Li0.2Co0.3Mn0.5]O2 electrode exhibits a pair of reversible redox peaks corresponding to lithium ion intercalation and deintercalation at the safe potential window without causing the electrolysis of water. CV experiments at various scan rates revealed a linear relationship between the peak current and the square root of scan rate for all peak pairs, indicating that the lithium ion intercalation–deintercalation processes are diffusion controlled. The corresponding diffusion coefficients are found to be in the order of 10?8?cm2?s?1. A typical cell employing Li[Li0.2Co0.3Mn0.5]O2 as cathode and LiTi2(PO4)3 as anode in 2?M Li2SO4 solution delivers a discharge capacity of 90?mA?h g?1. Electrochemical impedance spectral data measured at various discharge potentials are analyzed to determine the kinetic parameters which characterize intercalation–deintercalation of lithium ions in Li[Li0.2Co0.3Mn0.5]O2 from 2?M Li2SO4 aqueous electrolyte.  相似文献   

10.
Lithium metal has been considered as the most promising anode electrode for substantially improving the energy density of next‐generation energy storage devices. However, uncontrollable lithium dendrite growth, an unstable solid electrolyte interface (SEI), and infinite volume variation severely shortens its service lifespan and causes safety hazards, thus hindering the practical application of lithium metal electrodes. Here, carbon fiber film (CFF) modified by lithiophilic Co3O4 nanowires (denoted as Co3O4 Nws) was proposed as a matrix for prestoring lithium metal through a thermal infusion method. The homogeneous needle‐like Co3O4 nanowires can effectively promote molten lithium to infiltrate into the CFF skeleton. The post‐formed Co?Li2O nanowires produced by the reaction of Co3O4 Nws and molten lithium can homogeneously distribute lithium ions flux and efficaciously increase the adsorption energy with lithium ions proved by density functional theory (DFT) calculation, boosting a uniform lithium deposition without dendrite growth. Therefore, the obtained composite anode (denoted as CFF/Co?Li2O@Li) exhibits superior electrochemical performance with high stripping/plating capacities of 3 mAh cm?2 and 5 mAh cm?2 over long‐term cycles in symmetrical batteries. Moreover, in comparison with bare lithium anode, superior Coulombic efficiencies coupled with copper collector and full battery behaviors paired with LiFePO4 cathode are achieved when CFF/Co?Li2O@Li composite anode was employed.  相似文献   

11.
The reaction mechanism of CO oxidation on the Co3O4 (110) and Co3O4 (111) surfaces is investigated by means of spin‐polarized density functional theory (DFT) within the GGA+U framework. Adsorption situation and complete reaction cycles for CO oxidation are clarified. The results indicate that 1) the U value can affect the calculated energetic result significantly, not only the absolute adsorption energy but also the trend in adsorption energy; 2) CO can directly react with surface lattice oxygen atoms (O2f/O3f) to form CO2 via the Mars–van Krevelen reaction mechanism on both (110)‐B and (111)‐B; 3) pre‐adsorbed molecular O2 can enhance CO oxidation through the channel in which it directly reacts with molecular CO to form CO2 [O2(a)+CO(g)→CO2(g)+O(a)] on (110)‐A/(111)‐A; 4) CO oxidation is a structure‐sensitive reaction, and the activation energy of CO oxidation follows the order of Co3O4 (111)‐A(0.78 eV)>Co3O4 (111)‐B (0.68 eV)>Co3O4 (110)‐A (0.51 eV)>Co3O4 (110)‐B (0.41 eV), that is, the (110) surface shows higher reactivity for CO oxidation than the (111) surface; 5) in addition to the O2f, it was also found that Co3+ is more active than Co2+, so both O2f and Co3+ control the catalytic activity of CO oxidation on Co3O4, as opposed to a previous DFT study which concluded that either Co3+ or O2f is the active site.  相似文献   

12.
Sn-doped Li-rich layered oxides of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 have been synthesized via a sol-gel method, and their microstructure and electrochemical performance have been studied. The addition of Sn4+ ions has no distinct influence on the crystal structure of the materials. After doped with an appropriate amount of Sn4+, the electrochemical performance of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 cathode materials is significantly enhanced. The optimal electrochemical performance is obtained at x = 0.01. The Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode delivers a high initial discharge capacity of 268.9 mAh g?1 with an initial coulombic efficiency of 76.5% and a reversible capacity of 199.8 mAh g?1 at 0.1 C with capacity retention of 75.2% after 100 cycles. In addition, the Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode exhibits the superior rate capability with discharge capacities of 239.8, 198.6, 164.4, 133.4, and 88.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively, which are much higher than those of Li1.2Mn0.54Ni0.13Co0.13O2 (196.2, 153.5, 117.5, 92.7, and 43.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively). The substitution of Sn4+ for Mn4+ enlarges the Li+ diffusion channels due to its larger ionic radius compared to Mn4+ and enhances the structural stability of Li-rich oxides, leading to the improved electrochemical performance in the Sn-doped Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials.  相似文献   

13.
In this work, highly chemiluminescent magnetic mesoporous carbon with yolk-shell structure was synthesized by encapsulating N-(4-aminobutyl)-N-ethylisoluminol (ABEI) and Co2+ into the magnetic mesoporous carbon composites (Co2+-ABEI-Fe3O4@ void@C). The synthetic Co2+-ABEI-Fe3O4@void@C showed a good magnetic separation property, which could remove residual ABEI molecules and Co2+ in less than 3 min under an external magnet. Moreover, the synthetic Co2+-ABEI-Fe3O4@void@C demonstrated good chemiluminescence (CL) property and good stability when interacted with alkaline H2O2 solution. The CL intensity of such Co2+-ABEI-Fe3O4@void@C was about 120 times higher than that of ABEI-Fe3O4@void@C. The Co2+-ABEIFe3O4@ void@C also exhibited good electrochemiluminescence (ECL) property in alkaline solution. The outstanding CL/ECL performance of the Co2+-ABEI-Fe3O4@void@C was attributed to the Co2+ immobilized in the Co2+-ABEI-Fe3O4@void@C, which catalyzed the decomposition of H2O2 to generate O2?? and HO?, expediting the CL/ECL reaction. The synthetic Co2+-ABEI-Fe3O4@void@C may be of great application for the development of new methodologies in bioanalysis.  相似文献   

14.
Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O2 batteries, and are believed to form and decompose reversibly in metal‐O2/CO2 cells. In these cathodes, Li2CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+. However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2CO3→4 Li++4 e?+2 CO2+O2, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1O2 in metal‐O2 batteries, question the possibility of a reversible metal‐O2/CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li2CO3.  相似文献   

15.
The universal cathode crossover such as chemical and oxygen has been significantly overlooked in lithium metal batteries using high-energy cathodes which leads to severe capacity degradation and raises serious safety concerns. Herein, a versatile and thin (≈25 μm) interlayer composed of multifunctional active sites was developed to simultaneously regulate the Li deposition process and suppress the cathode crossover. The as-induced dual-gradient solid-electrolyte interphase combined with abundant lithiophilic sites enable stable Li stripping/plating process even under high current density of 10 mA cm−2. Moreover, X-ray photoelectron spectroscopy and synchrotron X-ray experiments revealed that N-rich framework and CoZn dual active sites can effectively mitigate the undesired cathode crossover, hence significantly minimizing Li corrosion. Therefore, assembled lithium metal cells using various high-energy cathode materials including LiNi0.7Mn0.2Co0.1O2, Li1.2Co0.1Mn0.55Ni0.15O2, and sulfur demonstrate significantly improved cycling stability with high cathode loading.  相似文献   

16.
CuL2 · 1.5H2O and ML2 · 2H2O · 2EtOH (M = Co2+, Ni2+, Mn2+) coordination compounds were synthesized via the exchange reaction between the sodium salt of 3-methyl-1-phenyl-4-formylpyrazol-5-one (HL) and metal chlorides.The synthesized compounds were studied by thermogravimetry, magnetochemistry, and electron and IR spectroscopy. The complexes CuL2 · 2Py and CoL2 · 2Py · MeOH were obtained via recrystallization from a methanol-pyridine mixture, and their structures were studied by X-ray diffraction. Pyrazolone was found to be coordinated in the deprotonated enol form and to form six-membered chelate rings with a metal. The coordination polyhedron of a metal cation was found to be a square bipyramid (Cu2+) or an axially elongated octahedron (Co2+) with its vertices occupied by the oxygen atoms of 3-methyl-1-phenyl-4-formylpyrazol-5-one and the nitrogen atoms of pyridine.  相似文献   

17.
Electroreduction of CO2 into hydrocarbons could contribute to alleviating energy crisis and global warming. However, conventional electrocatalysts usually suffer from low energetic efficiency and poor durability. Herein, atomic layers for transition‐metal oxides are proposed to address these problems through offering an ultralarge fraction of active sites, high electronic conductivity, and superior structural stability. As a prototype, 1.72 and 3.51 nm thick Co3O4 layers were synthesized through a fast‐heating strategy. The atomic thickness endowed Co3O4 with abundant active sites, ensuring a large CO2 adsorption amount. The increased and more dispersed charge density near Fermi level allowed for enhanced electronic conductivity. The 1.72 nm thick Co3O4 layers showed over 1.5 and 20 times higher electrocatalytic activity than 3.51 nm thick Co3O4 layers and bulk counterpart, respectively. Also, 1.72 nm thick Co3O4 layers showed formate Faradaic efficiency of over 60 % in 20 h.  相似文献   

18.
In this work we report an easy and efficient way to fabricate nanostructured cobalt oxide (Co3O4) thin films as a non-enzymatic sensor for H2O2 detection. Co3O4 thin films were grown on ITO glass substrates via the sol-gel method and characterized with several techniques including X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and optical absorbance. The Co3O4 thin films’ performance regarding hydrogen peroxide detection was studied in a 0.1 M NaOH solution using two techniques, cyclic voltammetry (CV) and amperometry. The films exhibited a high sensitivity of 1450 μA.mM−1.cm−2, a wide linear range from 0.05 μM to 1.1 mM, and a very low detection limit of 18 nM. Likewise, the Co3O4 thin films produced showed an exceptional stability and a high selectivity.  相似文献   

19.
《中国化学快报》2023,34(7):107777
CO oxidation is a benchmark in heterogeneous catalysis for evaluation of redox catalysts due to its practical relevance in many applications and the fundamental problems associated with its very high activity at low temperatures. Among which, Co3O4 is one of the most active non-precious metal catalysts. Exposed crystal planes and cobalt sites are considered to be important for its high catalytic activity. Herein, we demonstrate an enhanced CO oxidation activity by a defect-rich mesoporous Co3O4 that prepared by a designed dual-template method. Two different kinds of silicas are used as hard-templates at the same time, resulting in a defect-rich mesoporous Co3O4 with a surface area as high as 169 m2/g. This catalyst exhibited a very high catalytic activity for low temperature CO oxidation with a light-off temperature at −73 oC under the space velocity of 80,000 mL h-1 gcat-1. Further studies reveal that the high surface area promotes the lattice oxygen mobility, surface rich of Co2+ species and active oxygen species are crucial for the high catalytic activity. Moreover, the dual-template approach paves a way towards the design and construction of high-surface-area mesoporous metal oxides for various applications.  相似文献   

20.
A series of 2D isomorphous MOFs [M (HBTC)(BMIOPE)·DMF·H2O]n (M = Zn ( 1 ), Zn0.7Co0.3 ( 2 ), Zn0.5Co0.5 ( 3 ), Zn0.3Co0.7 ( 4 ), Co ( 5 ), H3BTC = 1,3,5-benzenetricarboxylic acid, BMIOPE = 4,4′-bis(2-methylimidazol-1-yl)diphenyl ether) were synthesized to investigate the correction between the center metal ions and the photocatalytic behaviors. The photocatalytic results show that with the increase of Co2+ content, the photodegradation properties are continuously improved from 1 to 5 , which fully indicate that only changing metal ions could regulate the photodegradation properties. In detail, 1 is an inactive photocatalyst to degrade methylene blue (MB), while 5 exhibits preeminent photocatalytic properties under visible light irradiation. Moreover, 1 shows good selective sensing toward Fe3+, Cr3+, UO22+, CrO42− and Cr2O72− ions in aqueous solution. To the best of our knowledge, 1 is the first MOF example for the optical detection of Fe3+, Cr3+, UO22+, CrO42− and Cr2O72− ions in aqueous solution.  相似文献   

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