CN116351423B - Cu-Co3O4Catalyst, preparation method and application thereof - Google Patents
Cu-Co3O4Catalyst, preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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Abstract
The invention discloses a Cu 2+ doped octahedral Co 3O4 nano material prepared by adopting a coprecipitation method and a calcination process (Cu-Co 3O4).Cu-Co3O4 has higher peroxidase catalytic activity than pure octahedral Co 3O4, and the catalytic kinetics of the octahedral Cu-Co 3O4 follows a typical Mies kinetic equation and has strong affinity (K m = 0.0706 mM) to TMB). Based on the octahedral Cu-Co 3O4, a simple and efficient GSH colorimetric sensing platform is constructed, the linear range of the colorimetric sensing platform is 1-60 mu M, the lowest detection limit is 0.53 mu M, and the method has good selectivity for detecting GSH.
Description
Technical Field
The invention relates to a chemical catalyst and a preparation method thereof, in particular to a method for preparing Cu 2+ doped octahedral Co 3O4(Cu-Co3O4 by adopting a simple coprecipitation method and a calcination process, which is used for simulating peroxidase and detecting the content of glutathione in a human serum sample.
Background
Glutathione (GSH) is a thiol-containing tripeptide (glutamate, cysteine, and glycine) that is involved in metabolism of animals and plants, including regulating intracellular signal transduction and maintaining cellular redox balance. In general, tripeptides are in two forms: reduced form (GSH) and oxidized form (GSSG). Particularly, reducing GSH prevents oxidation of hemoglobin, thereby maintaining normal oxygen transport. Thus, abnormalities in GSH levels in organisms are closely related to disease risk and health conditions, such as cancer, cystic fibrosis, skin damage, and heart disease. Therefore, GSH detection in biological samples has become an important task.
Cobalt oxide (Co 3O4) is one of the transition metal oxides with mixed valence spinel structure, with unique chemical and physical properties. The Co 3O4 nano material is reported to have the characteristic of intrinsic similar enzyme, and has wide application prospect in the field of biosensing. For example, mu et al found that Co 3O4 nanoparticles having both peroxidase-like and catalase-like properties can be used in colorimetric glucose assays. However, promoting the enzyme-like activity of Co 3O4 nanomaterials remains a significant challenge in practical applications. In order to increase the enzyme activity, researchers have prepared a variety of Co 3O4 -based nanomaterials by different methods. Among them, metal ion doping is considered as one of the most common effective strategies, and has been applied to various colorimetric detection. Doping with transition metal ions is considered to be one of the most effective means for optimizing the catalytic efficiency of metal oxides.
In 2018, lu et al prepared Mo 6+ -doped Co 3O4 nanotubes (Mo-Co 3O4) by electrospinning in combination with calcination, and the prepared Mo-Co 3O4 had more excellent peroxidase activity than pure Co 3O4 nanotubes. When the doping ratio is less than 5.0%, mo 6+ replaces Co 3+ or Co 2+ in the Co 3O4 lattice or exists as an amorphous substance, and the material crystal form is unchanged. At a mole fraction doping ratio of 2.0%, the Co 3O4 nanotubes had the highest peroxidase activity. Based on the high catalytic efficiency of the Mo-Co 3O4 nano tube, a simple, convenient and efficient L-cysteine sensitive colorimetric detection method is developed, and the minimum detection limit is 24.2nM. The work provides a general thought for improving the activity of peroxidase and expands the application of the nano material in colorimetric sensing, disease diagnosis and environmental monitoring, but the existing nano material has the problems of weak enzyme catalytic activity, insufficient fine structure, complex preparation process and poor reusability.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides a method for preparing Cu 2+ -doped octahedral Co 3O4 nanomaterial (Cu-Co 3O4) by adopting a coprecipitation method and a calcination process, wherein Cu-Co 3O4 has higher peroxidase catalytic activity than pure octahedral Co 3O4 and can be used for detecting the content of glutathione in human serum samples.
In order to achieve the above object, the present invention provides the following technical solutions:
A Cu-Co 3O4 catalyst, the Cu-Co 3O4 catalyst being prepared using a Co-precipitation combined with calcination process, and the Cu-Co 3O4 catalyst having an octahedral shape. The doped nano material has a hollow structure, has the advantages of large specific surface area, multiple catalytic active sites and the like, and is beneficial to improving the activity of peroxidase.
The invention also requests a preparation method of the Cu-Co 3O4 catalyst, which specifically comprises the following steps:
(1) 2-5mmol of CoCl 2·6H2 O and CuSO 4·5H2 O (0, 1.0, 2.0, 4.0, 6.0, 8.0 and 10.0%) with magnetic stirring at 50-90 ℃ are dissolved in 10mL of absolute ethanol, then 0.24mol/L (total volume of solution is 50 mL) of ammonium oxalate solution is added to 40mL of the mixed solution, and stirring is carried out until a uniform pink solution is formed;
(2) After the magnetic stirring at 50-90 ℃ is continued to react for 1-6 hours, respectively washing with deionized water and ethanol for three times, filtering, and placing the sample in a vacuum drying oven at 60 ℃ for drying for 12 hours; and finally, transferring the dried sample into a crucible, and placing the crucible in a muffle furnace at 300-600 ℃ to calcine for 2-5h to obtain Cu-Co 3O4 NPs with different Cu 2+ doping ratios.
The invention also discloses application of the Cu-Co 3O4 catalyst in qualitative and quantitative detection of glutathione.
Compared with the prior art, the Cu-Co 3O4 catalyst, the preparation method and the application thereof provided by the invention have the following excellent effects:
The invention adopts a simple coprecipitation method and calcination process to prepare Cu 2+ doped octahedral Co 3O4(Cu-Co3O4) for simulating peroxidase. Doping with transition metal elements helps to increase the catalytic efficiency of the peroxidase-like enzyme. Compared with single Co 3O4, the prepared octahedral Cu-Co 3O4 has higher catalytic activity than single Co 3O4. The doped nano material has a hollow structure, has the advantages of large specific surface area, multiple catalytic active sites and the like, and is beneficial to improving the activity of peroxidase.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 (a) Cu-Co 3O4 XRD patterns with different doping ratios; (b) a locally amplified XRD pattern of 35 ° to 39 °.
FIG. 2 (a) Raman spectra of Cu-Co 3O4 with different doping ratios; (b) 550-750 cm -1.
FIG. 3 shows Cu 2+ doping ratios of (a) 0%, respectively; (b) 1.0%; (c) 2.0%; (d) 4.0%; (e) 6.0%; (f) 8.0% and (g) 10.0% Cu-Co 3O4 SEM and TEM pictures.
FIG. 4 is a TEM image of Cu-Co 3O4 with a 6% Cu 2+ doping ratio of 6%. (a-c) TEM images of Cu-Co 3O4 (6%) at different magnifications; (d) HRTEM images of Cu-Co 3O4 (6%); (e) selecting an electron diffraction pattern (SAED); (f) EDX spectrum and elemental composition of Cu-Co 3O4 (6%).
FIG. 5 (a) XPS total spectrum of Cu-Co 3O4 NPs; (b) high resolution spectra of Co 2 p; (c) high resolution spectra of Cu 2 p; (d) high resolution spectra of O1 s.
FIG. 6 (a) N 2 adsorption-desorption isotherms of Co 3O4,(b)6.0％Cu-Co3O4 NPs and corresponding pore size distribution.
FIG. 7 shows the UV-visible spectrum of (1)TMB,(2)OPD,(3)ABTS,(4)TMB+Cu-Co3O4+H2O2,(5)OPD+Cu-Co3O4+H2O2,(6)ABTS+Cu-Co3O4+H2O2 for the color substrates, respectively.
FIG. 8 (a) is a graph of UV-Vis spectra of different systems; (b) TMB chromogenic reaction equation; (c) Uv-vis absorption spectra of Cu-Co 3O4 with different doping ratios in acetate buffer (ph=4.0) for 20 minutes; (d) Cu-Co 3O4 catalytic activity versus Cu 2+ mole fraction.
FIG. 9 (a) effect of isopropanol and p-benzoquinone on TMB oxidation; (b) 6% Cu-Co 3O4 and Co 3O4 DMPO spin-trapping · OH EPR spectra.
FIG. 10 (a) stability of catalytic activity of Cu-Co 3O4 -type peroxidases under optimal conditions; (b) Stability of Cu-Co 3O4 to oxidase-like catalytic activity of 60. Mu.M GSH under optimal conditions. Error bars represent standard deviation of three measurements.
FIG. 11 (a) UV-visible spectrum of solutions at different pH values; (b) influence of pH; (c) the ultraviolet-visible spectrum of the solution at different temperatures; (d) influence of temperature; (e) Ultraviolet-visible spectrum of the solution at different reaction times; (f) effect of reaction time on absorbance; error bars represent standard deviation of three measurements.
FIG. 12 (a) UV-visible spectra of solutions at different catalyst concentrations; (b) influence of catalyst concentration; (c) the ultraviolet-visible spectrum of the solution at different TMB concentrations; (d) effect of TMB concentration; (e) Ultraviolet-visible spectrum of the solution at different concentrations of H 2O2; (f) Effect of H 2O2 concentration; error bars represent standard deviation of three measurements.
FIG. 13 is a steady state kinetic analysis of Cu-Co 3O4 NPs. (a) H 2O2 concentration was fixed at 15mM and TMB concentration was different; (b) a Lineweaver-Burk double reciprocal plot corresponding to (a). (c) TMB concentration was fixed at 80. Mu.M, H 2O2 concentrations varied; (d) a Lineweaver-Burk double reciprocal plot corresponding to (c).
FIG. 14 is a colorimetric detection of GSH. (a) Ultraviolet-visible spectrum chart of Cu-Co 3O4 -GSH-TMB system after adding GSH solution with different concentration; (b) Colorimetric determination of absorbance at 652nm with different concentrations of GSH (0-200. Mu.M) photographs of the solutions after addition of different concentrations of GSH (increasing from left to right); (c) The linear relationship with GSH concentration was between 1 and 65. Mu.M (inset: corresponding color change of solution). (d) GSH is selective for potential interference; error bars represent standard deviation of three measurements.
Fig. 15 is a schematic diagram of the detection principle.
FIG. 16 shows the relative activity of Cu-Co 3O4 cycles under optimal conditions.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a preparation method of Cu-Co 3O4.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
2Mmol of CoCl 2·6H2 O and various mole fractions of CuSO 4·5H2 O (2.0%) were dissolved in 10mL of absolute ethanol under magnetic stirring at 60℃and then 40mL of an ammonium oxalate solution (0.24 mol/L total volume of solution 50 mL) was added to the above mixed solution and stirred until a uniform pink solution was formed. After the magnetic stirring at 60 ℃ is continued to react for 2 hours, washing with deionized water and ethanol for three times respectively, filtering, and drying the sample in a vacuum drying oven at 60 ℃ for 12 hours; finally, transferring the dried sample into a crucible, and placing the crucible in a muffle furnace at 300 ℃ to calcine for 3 hours to obtain Cu 2+ doped Cu-Co 3O4 NPs.
Example 2
This embodiment differs from embodiment 1 in that: 2mmol of CoCl 2·6H2 O is modified into 3mmol of CoCl 2·6H2 O under magnetic stirring at 70 ℃ and 80 ℃ under magnetic stirring, and the rest process steps and process parameters are unchanged.
Example 3
This embodiment differs from embodiment 1 in that: the "different mole fractions of CuSO 4·5H2 O (2.0%) were dissolved in 10mL of absolute ethanol" was modified to "different mole fractions of CuSO 4·5H2 O (6.0%) were dissolved in 10mL of absolute ethanol", the remaining process steps and process parameters being unchanged.
Example 4
This embodiment differs from embodiment 1 in that: the process is modified from 'calcining for 3 hours in a muffle furnace at 300 ℃ to' calcining for 3 hours in a muffle furnace at 400 ℃ and the rest process steps and process parameters are unchanged.
Example 5
This embodiment differs from embodiment 1 in that: the process is modified from 'calcining for 3h in a muffle furnace at 300 ℃ to' calcining for 4h in a muffle furnace at 500 ℃ and the rest process steps and process parameters are unchanged.
Example 6
This embodiment differs from embodiment 1 in that: after the magnetic stirring at 60 ℃ is continued for 2 hours, the magnetic stirring at 80 ℃ is modified to be continued for 4 hours, and the rest process steps and process parameters are unchanged.
The technical scheme is verified and tested as follows:
1. Materials and methods
(1) Experimental reagent and material
Cobalt nitrate hexahydrate (Co (NO 3)2·6H2 O, analytically pure, the company, inc. Of the sciences of the ridge); 3,3', 5' -tetramethylbenzidine (TMB, analytical grade, shanghai Biochemical technologies Co., ltd.), disodium hydrogen phosphate (NaH 2PO4·2H2 O, analytical grade, tianjin chemical Co., ltd.), citric acid (C 2H2O7, analytical grade, tianjin chemical Co., ltd.), copper sulfate pentahydrate (CuSO 4·5H2 O, analytical grade, tianjin chemical Co., ltd.), glutathione (GSH, analytical grade, tianjin Obo chemical Co., ltd.), tryptophan (TRP, analytical grade, tianjin Obo chemical Co., ltd.), methionine (Met, analytical grade, tianjin Obo chemical Co., ltd.), phenylalanine (Phe, analytical grade, tianjin Obo chemical Co., ltd.), isopropyl alcohol (IPA, analytical grade, tianjin chemical Co., ltd.), quinone (BQ, analytical grade, tianjin chemical Co., ltd.), glacial acetic acid (HAc, tianjin chemical Co., ltd.), sodium acetate (Ac, najin chemical Co., ltd.), and Najin chemical Co., ltd.
(2) Laboratory instrument and apparatus
SU-8010 field emission scanning electron microscope (japanese hitachi); JEM-2100 transmission electron microscope (Hitachi, japan); thermo fisher laser raman spectrometer (DXR 532 nm); 722S visible spectrophotometer (Shanghai precision scientific instruments Co., ltd.); D/MAX 2500TC X-ray diffractometer (Japanese society Co.); UV-1800PC ultraviolet-visible spectrophotometer (Shanghai analytical spectroscopy instruments limited); UPR-II-10T ultra-pure water machine (Chengdu ultra-pure technology Co., ltd.); TGL-10B high-speed bench centrifuge (Shanghai Anting scientific instruments).
(3) Experimental method
(1) Preparation of Cu 2+ -doped Co 3O4 particles
2Mmol of CoCl 2·6H2 O and various mole fractions of CuSO 4·5H2 O (0, 1.0, 2.0, 4.0, 6.0, 8.0 and 10.0%) were dissolved in 10mL of absolute ethanol with magnetic stirring at 80℃and then 40mL of an ammonium oxalate solution of 0.24mol/L (total volume of solution 50 mL) was added to the above mixed solution and stirred until a uniform pink solution was formed. The doping ratio of Cu 2+ is calculated according to formula (1):
After the magnetic stirring at 80 ℃ is continued to react for 2 hours, washing with deionized water and ethanol for three times respectively, filtering, and drying the sample in a vacuum drying oven at 60 ℃ for 12 hours; finally, transferring the dried sample into a crucible, and placing the crucible in a muffle furnace at 400 ℃ to calcine for 3 hours to obtain Cu-Co 3O4 NPs with different Cu 2+ doping ratios.
(2) Peroxidase-like Activity Studies of Cu-Co 3O4
50. Mu.L of Cu-Co 3O4 nanoparticle suspension (2 mg/mL) was added as a catalyst to acetate buffer with pH of 4.0, 20. Mu.L of TMB solution (8 mM in ethanol) was added, and finally 30. Mu.L of H 2O2 (1M) solution was added to start the reaction system, and after reacting at room temperature for 20min, the absorbance value of the reaction system at 652nm was measured by an ultraviolet-visible spectrometer. In order to explore the influence of environmental parameters on the catalytic performance, the influence of the pH value and the temperature of the acetic acid buffer solution on the catalytic performance is examined.
In addition, steady state kinetics study is also carried out on the catalytic performance of the material, and firstly, in the reaction system, the kinetic parameters of TMB are obtained by fixing the concentration of H 2O2 to 15 mM. Likewise, the TMB concentration was fixed at 8. Mu.M, and the H 2O2 concentration was adjusted to find the kinetic parameters of H 2O2. The apparent kinetic parameters were calculated using the mie equation and the double reciprocal curve:
Wherein V is the initial reaction speed, V max is the maximum reaction speed, K m is the Mi constant, and [ S ] is the substrate concentration.
(3) Colorimetric detection of GSH
The peroxidase activity of Cu-Co 3O4 NPs was achieved by adding 80. Mu.M TMB as chromogenic substrate to acetate buffer (pH 4.0). First, 50. Mu.L of Cu-Co 3O4 solution (50. Mu.g/mL) was mixed with 1898. Mu.L of HAc-NaAc buffer (pH 4.0), incubated at room temperature for 3min, and then 20. Mu.L (8 mM) of TMB solution and 30. Mu.L (1M) of H 2O2 were added, colorless TMB was converted to blue (oxTMB) solution, and absorbance at 652nm was significantly increased. Then 2. Mu.L of GSH solution of different concentrations was added, the final concentration of glutathione was 0-200. Mu.M. The solution changed from blue to colorless due to the reducibility of GSH. After 20min, the absorbance value of the reaction system was measured at 652nm, and then the concentration of GSH was calculated according to lambert-beer law.
To determine the selectivity of the assay, the absorbance values of the system were determined using 5 metal ions (Ba 2+、Mg2+、Zn2+、Mn2+、Fe3+) and six amino acids as interfering substances using the method described above. The amino acid concentration in the experiment was 200. Mu.M. The metal ion concentration was 2mM.
(4) Actual sample analysis
The recovery rate of GSH is mainly analyzed by a labeled recovery method. According to the recovery (%) = (addition standard sample measurement value-sample measurement value)/addition standard amount×100%. mu.L (2 mg/mL) of Cu-Co 3O4 NFs, 20. Mu.L (8 mM) of TMB and 30. Mu.L (1M/L) of H 2O2 were added to an acetate buffer solution at pH 4.0. After 3min of reaction at 30℃10. Mu.L of human serum sample was added followed by different concentrations of glutathione. Sufficiently shaking to uniformly mix the materials. The mixed solution was incubated at 30℃for 20min, and then the glutathione concentration was detected at 652nm using an ultraviolet-visible absorption spectrometer. In order to verify the accuracy of the colorimetric method for detecting GSH, high performance liquid chromatography is used for comparison.
(5) Relative Activity (%)
The relative activity was calculated from the following formula:
Relative activity (%) =a i/A1 ×100% (3)
Where A 1 is the absorbance value measured at 652nm for the first cycle of the system and A i is the absorbance value measured at 652nm for the ith cycle under the same conditions. In the above experiments, the correlation results were converted to relative activities for convenient mapping, with the point of maximum activity set at 100%.
(6) Characterization method
The morphology and structure of the composite material were characterized using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). And according to the electron microscope photo, the morphology and structure of the material are regulated and controlled by adjusting the preparation method of the material. The crystal structure of the sample Cu-Co 3O4 NPs particles was characterized by X-ray diffraction (XRD). The chemical state and surface elemental composition of Cu-Co 3O4 NPs particles were measured using X-ray photoelectron spectroscopy (XPS). The surface functional groups of the prepared material are characterized by adopting Fourier transform infrared spectroscopy (FT-IR). And (3) carrying out nitrogen adsorption and desorption characterization on the prepared material by adopting a particle physical adsorption analyzer, and further obtaining data such as specific surface area, pore volume, pore diameter and the like of the material. And detecting the absorption curve of the solution by adopting ultraviolet-visible light (UV-vis) to obtain the absorbance value of the maximum absorption wavelength. The Raman spectrum analyzer is mainly used for researching the vibration state of the crystal lattice and the defects of the material, so that the properties of the substances are further verified. An electron paramagnetic resonance spectrometer (EPR) is adopted to mainly capture oxygen active species generated in the catalytic process of the material, and an EPR experiment is carried out by taking DMPO as a spin capturing agent.
2. Analysis of results
(1) Structural characterization analysis of Cu-Co 3O4
The effect of different doping ratios of Cu 2+ on the crystal structure of Cu-Co 3O4 NPs was examined by X-ray diffraction (XRD). As can be seen from FIG. 1 (a), at a doping ratio of 0-8%, XRD diffraction peaks of the Cu-Co 3O4 NPs sample are substantially identical, and peaks at 18.74 °, 31.28 °, 36.74 °, 38.51 °, 44.73 °, 55.54 °, 59.43 °, 65.18 °, 77.54 ° are respectively assigned to (111), (220), (311), (222), (400), (422), (511), (440), and (533) crystal planes, corresponding to standard card PDF#73-1701 (cuboid, fd-3m, Α=90°), which is attributable to the spinel Co 3O4 crystal structure, indicating that moderate doping does not affect the crystal structure of Co 3O4. However, as the Cu 2+ doping ratio reached 10.0%, the sample showed a distinct diffraction peak at 25.46 °, indicating that at higher doping ratios the Cu species could not be fully doped in the crystal structure of Co 3O4, resulting in the formation of other new species. Fig. 1 (b) shows the partially enlarged XRD pattern of fig. 1 (a), and it is clearly observed that the typical diffraction peak of Co 3O4 shifts to a lower extent at about 36.74 ° when the doping ratio is increased from 0% to 10%, due to the difference between the ionic radii of Co and doped Cu, resulting in lattice deformation of the product after doping of Cu species.
To further confirm the successful doping of Cu, cu-Co 3O4 NPs were analyzed by Raman spectroscopy. As shown in FIG. 2, typical peak positions for Cu-Co 3O4 NPs with different doping ratios are similar, and peaks at 190, 478, 518, 617cm -1 can be assigned to the F 2g 1、F2g 2、F2g 3 and A g 1 Raman activity modes of Co 3O4 nanocrystals, respectively, corresponding to lattice-vibrating Co 2+ and Co 3+, respectively. Further, it can be clearly observed from the amplified Raman spectrum that the Raman peak of Cu-Co 3O4 NPs shifts to the high wavenumber direction in the range of 630 to 720cm -1. It is well known that the position of the peak in the raman spectrum is related to the stress in the crystal, in particular, compressive stress shifts the peak to higher wavenumbers, while tensile stress shifts the peak to lower wavenumbers. The results indicate that there is compressive stress in the Cu-Co 3O4 NPs due to lattice distortion caused by the different radii of the Cu and Co elements due to the doping of Cu ions into the Co 3O4 lattice. In addition, the peak bias of the samples with different doping ratios is consistent with the XRD spectrum.
The influence of changing the Cu 2+ doping ratio on the morphology and the catalytic activity of the octahedral Cu-Co 3O4 is studied. Fig. 3 shows SEM and TEM images of octahedral Cu-Co 3O4 with different doping ratios, from which it can be clearly observed that the surface morphology of the octahedral Cu-Co 3O4 changes with increasing doping ratio of Cu 2+. When the doping ratio is less than 6% (fig. 3 (a-e)), the cu—co 3O4 has a diameter of about 1 μm, and is still an octahedral structure, and the morphology is not changed much. However, as the doping ratio of Cu 2+ increases, the size of the octahedron changes significantly. When the doping ratio of Cu 2+ is 1%, 2% and 4%, the diameter of the octahedral Cu-Co 3O4 is gradually reduced, when the doping ratio of Cu 2+ reaches 6%, the diameter of the octahedral Cu-Co 3O4 is smaller, about 50nm is reached, the smaller particles are, the larger specific surface area of the material is, and a large number of catalytic reaction active sites can be provided for the reaction.
When the doping ratio of Cu 2+ reached 8% -10% (fig. 3 (f-g)), it was clearly observed from SEM and TEM images of Cu-Co 3O4 that the structure of the material was no longer octahedral, but rather a large number of blocks or plate-like morphologies were self-assembled from smaller particles, and the agglomeration phenomenon was severe. The main reason for this phenomenon is that (1) after the particles reach the nanometer level, a large amount of positive and negative charges are accumulated on the surfaces of the particles, and charge aggregation is caused; (2) As the nanoparticle size decreases, the proportion of surface atoms of the nanoparticle increases rapidly, and when the nanoparticle size decreases to a certain extent, the surface atoms are almost all concentrated on the surface of the particle and are in a highly activated state, resulting in insufficient coordination number of the surface atoms and high surface energy; (3) The nano particles have high chemical activity, show strong surface effect, and are easy to reduce the surface energy through aggregation to reach the stable state with the lowest energy. Because large-shaped sheets or blocky particles formed by agglomeration are uneven in size and disordered in morphology, the catalytic performance of the material is weaker.
The TEM image reveals more clearly the surface morphology and microstructure of the Cu-Co 3O4 material. Fig. 4 (a-c) shows TEM pictures of octahedral Cu-Co 3O4 with a doping ratio of 6% for Cu 2+ at different magnifications. As can be seen from the figure, after doping with 6% Cu 2+, the material exhibits an octahedral structure with a diameter of about 50nm. Afterwards, the detailed crystal structure and chemical composition of Cu-Co 3O4 were characterized using HRTEM. In fig. 4 (d), the typical HRTEM of octahedral Cu-Co 3O4 shows clear lattice fringes, indicating high crystallinity of the sample, with lattice spacings d= 0.2859nm and d= 0.2437nm corresponding to the (220) and (311) crystal planes (JCPDS No. 73-1701), respectively. Furthermore, the (220), (311) and (511) diffraction patterns of Co 3O4 were clearly observed from the Selected Area Electron Diffraction (SAED) pattern (FIG. 4 (e)), indicating that doping Cu 2+ did not alter the crystal structure of Co 3O4, and Cu-Co 3O4 was present as a pure phase. Fig. 4 (f) shows EDX spectrum analysis of octahedral Cu-Co 3O4 (6%), from which it is seen that O, cu and Co elements are present in the material, and the mass percentages of the three are 60.64%, 2.58% and 36.78%, respectively, the atomic percentages are 56.27%, 1.88% and 41.85%, respectively, the molar ratio of O and Co is close to 4:3, and is well-fitted with an octahedral Cu-Co 3O4 with a molar doping ratio of 6%, confirming that 6% of Cu 2+ has been successfully doped inside the octahedral Co 3O4.
The surface properties and elemental valence states of Cu-Co 3O4 were studied using X-ray photoelectron spectroscopy (XPS). Fig. 5 (a) is a broad scan measurement spectrum of a material showing the presence of Cu, co, C, O elements. Fig. 5 (b) is a high resolution XPS spectrum of Co 2 p. From the figure, it can be seen that there are two main peaks, with binding energies 778.7eV and 794.6eV, corresponding to Co 2p 3/2 and Co 2p 1/2, respectively. By gaussian fitting, the principal peak was deconvolved into 4 sub-peaks, of which two sub-peaks with binding energies 793.8 and 778.7eV were attributable to Co 3+, 795.0 and 779.8eV, and in turn to Co 2+, indicating that Co 3O4 was synthesized. In addition, two satellite peaks also appear, with binding energies at 787.7 and 803.2eV, respectively. FIGS. 2-5 (c) are high resolution XPS spectra of Cu 2p, with two peaks at binding energies 953.3eV and 933.3eV corresponding to Cu 2p 1/2 and Cu 2p 3/2, respectively, and a 20.0eV difference between the two peaks, which is a typical peak for Cu 2+ in materials. At the same time, three satellite peaks were observed at 940.5, 942.9, and 947.8eV, indicating the paramagnetic chemical state of Cu 2+. FIG. 5 (d) is a high resolution XPS spectrum of O1s, from which it can be clearly seen that the O1s spectrum fits into two peaks, located near 528.9eV and 530.4eV, respectively, corresponding to lattice oxygen (O latt) of metal oxide (M-O) and adsorbed oxygen (O ads) from hydroxyl groups to the surface of metal (M-OH), respectively.
FIG. 6 is a graph showing N 2 adsorption-desorption isotherms of Co 3O4 alone (FIG. 6 (a)) and Cu-Co 3O4 NPs (FIG. 6 (b)) with a doping ratio of 6.0% and the corresponding pore size distribution curves. As can be seen from fig. 6: the N 2 adsorption-desorption isotherms of the two materials were type IV, indicating that mesoporous structures were present in both materials. The occurrence of mesoporous pore canal is beneficial to mass transfer between the substrate and the product. Table 1 shows BET specific surface areas and corresponding pore volumes of the two materials, from which it can be seen that the specific surface areas and pore diameters of pure Co 3O4 are 34.25m 2/g and 11.46nm, respectively, and the specific surface areas and pore diameters of Cu-Co 3O4 NPs are better than pure Co 3O4, respectively, with doping ratios of 6.0% of Cu-Co 3O4 NPs of 69.78m 2/g and 8.44nm, respectively. The results show that the high specific surface area and the porous structure of the Cu-Co 3O4 NPs enable the contact area between the solution and the catalyst to be larger, and more active sites are provided for the catalytic reaction, so that the catalytic performance of the catalyst is enhanced.
Table 1 specific surface area and pore volume of samples
(2) Peroxidase-like Activity of Cu-Co 3O4 NPs
1) Catalytic Activity of Cu-Co 3O4 with different substrates
TMB, OPD and ABTS are three commonly used substrates for immunoassays and NP peroxidase-like activity evaluation. Therefore, we used the three substrates to verify the peroxidase activity of Cu-Co 3O4 NPs. Mixing octahedral Cu-Co 3O4 and H 2O2 with TMB (0.2 mM), ABTS (0.2 mM), OPD (0.2 mM) matrices, respectively, cu-Co 3O4 NPs can rapidly catalyze the typical oxidation reactions of TMB, OPD and ABTS in the presence of H 2O2, yielding characteristic blue, yellow and green products, respectively, in 20min (FIG. 7), indicating that Cu-Co 3O4 NPs have peroxidase-like activity similar to HRP. It was also found that the color change of the reaction system was most pronounced when TMB was used as the substrate, and the absorbance at 652nm was the greatest. In addition, TMB is less toxic than ABTS and OPD. Thus, TMB was chosen as the substrate for subsequent studies.
2) Effect of Cu 2+ doping ratio on catalytic activity of material
The catalytic activity of Cu-Co 3O4 NPs was studied mainly by adding the substrates TMB and H 2O2 to different reaction systems. As shown in FIG. 8 (a), when there is only TMB and HAc-NaAc buffer solution at pH4.0 in the reaction system, there is no absorption peak at 652 nm; when a certain amount of Co 3O4 and TMB or Cu-Co 3O4 and TMB (50. Mu.g/mL catalyst, 20. Mu.L 8mM TMB, HAC-NaAc buffer solution at pH 4.0) was added to the system, there was almost no absorbance at 652nm, indicating that the peroxidase-like activity of pure Co 3O4 was weak; when a certain amount of Co 3O4, TMB and H 2O2 (50. Mu.g/ml catalyst, 20. Mu.L of 8mM TMB, 30. Mu.L of 1M H 2O2, pH4.0 HAc-NaAc buffer solution) was added to the system, the absorbance of the solution at 652nm increased significantly, with an increase of 211% in the absence of H 2O2. After adding a certain amount of Cu-Co 3O4, TMB and H 2O2 (50. Mu.g/ml catalyst, 20. Mu.L of 8mM TMB, 30. Mu.L of 1M H 2O2, HAC-NaAC buffer pH 4.0) to the system, the absorbance of the solution increased significantly, 2.47 times the absorbance under Co 3O4+TMB+H2O2 system. The prepared Cu-Co 3O4 NPs are obviously enhanced in the activity of the peroxidase. The main reason for this is probably that the Cu doping resulted in a significant absorbance difference, indicating that Cu-Co 3O4 NPs could better catalyze the rapid oxidation of TMB. FIG. 8 (b) reflects the chemical reaction equation of the color development process.
Next, a control experiment was further performed to evaluate the catalytic activity of Cu-Co 3O4 NPs with different content copper doping ratios (fig. 8 (c)). After 20min of reaction, the maximum absorbance value of pure Co 3O4 at 652nm is 0.423, which indicates that pure Co 3O4 has certain peroxidase-like activity. With the increase of the doping proportion of Cu 2+ (1% -10%), the absorbance value of Cu-Co 3O4 NPs at 652nm shows a trend of increasing and then decreasing, when the doping proportion is 6%, the absorbance value reaches the maximum value, which is 1.046, which indicates that the prepared Cu-Co 3O4 NPs have the strongest catalytic performance when the doping proportion of Cu 2+ is 6%. This is due to the fact that moderate doping will lead to more lattice defects in Co 3O4, resulting in a decrease in fermi level and an increase in active sites during catalysis. These reactive sites facilitate improved electron transport efficiency, making it easier to consume H 2O2 to generate oxygen reactive species (ROS), rendering Cu-Co 3O4 NPs more susceptible to catalytic oxidation of TMB. In order to more intuitively show the effect of doping Cu elements in different proportions on the catalytic activity of the sample, fig. 8 (d) plots the doping ratio dependence in fig. 8 (c). It is apparent that the enzyme activity of Cu-Co 3O4 NPs doped at 6.0% is 147.28% higher than that of pure Co 3O4. Therefore, cu-Co 3O4 NPs with a doping ratio of 6.0% was chosen as the best catalyst for subsequent studies.
Table 2 shows the comparison of the enzymatic properties of the composite material before and after doping with the transition metal elements, as can be seen from the table: after the material is doped with a proper amount of hetero atoms, the enzyme activity is improved to different degrees, which indicates that the catalytic performance of the enzyme can be improved to a certain extent by doping a proper amount of hetero atoms.
TABLE 2 comparison of enzymatic Properties of transition metal doped materials
3) Reaction mechanism research
It is well known that the peroxidase-like properties of nanomaterials are attributed to the generation of ROS by the decomposition of H 2O2 by a catalyst, and in general, hydroxyl radicals (·oh) and superoxide radicals (O 2 ·-) are typical ROS in the peroxide-like reaction of nanomaterials. To investigate the major reactive oxygen species in the catalytic reaction, the experiments selected methods of isopropanol identification · OH and benzoquinone identification O 2 ·-. As can be seen from FIG. 9 (a), the color change was not large after adding equal amounts of 20mM isopropyl alcohol and benzoquinone, whereas the solution changed from blue to colorless after adding 200mM benzoquinone and isopropyl alcohol. The results show that O 2 ·- and small amounts of · OH contribute significantly to the catalytic reaction.
In general, EPR can measure unpaired electrons, such as O sites. Therefore, to further verify the production of · OH and O 2 ·- during catalysis, EPR experiments were performed with DMPO as spin trap. In general, spin magnitude is proportional to the strength of the EPR signal. As shown in FIG. 9 (b), in the system with Co 3O4 alone and Cu-Co 3O4 NPs complex as catalyst, characteristic peaks of DMPO- · OH with intensity of 1:2:2:1 were detected, confirming the presence of · OH. And the signal intensity of 6% Cu-Co 3O4 is far higher than that of a pure Co 3O4 system. Since O 2 ·- is less reactive to DMPO and to avoid interference with · OH in aqueous solution, O 2 ·- was chosen to be detected in methanol. It was found that EPR signal of DMPO-O 2 ·- was detected at an intensity of 1:1:1:1 in the Co 3O4 and 6% Cu-Co 3O4 systems, and that the latter signal intensity was stronger.
The results indicate that the 6% cu-Co 3O4 composite material can produce more O 2 ·- and · OH in the catalytic process than Co 3O4, and thus catalytic oxidation of TMB can be achieved more effectively.
4) Catalytic stability study of Cu-Co 3O4 NPs materials
The experiment also investigated the catalytic stability of Cu-Co 3O4. Under optimal conditions, the absorbance change at 652nm of oxTMB over 60 days was negligible (FIG. 10 (a)), indicating that the catalytic capacity of Cu-Co 3O4 was stable. Further, stability of the peroxidase catalytic activity of Cu-Co 3O4 in detecting GSH was examined (FIG. 10 (b)). When 60. Mu.M GSH was added, the absorbance at 652nm was drastically reduced from 1.046 to 0.032, since GSH had some reducibility and was able to reduce oxTMB to TMB, the color of the solution was changed from blue to colorless, resulting in a sharp drop in absorbance at 652 nm. After the reaction was completed and observed for another 3 minutes, the absorbance was unchanged, indicating that the catalytic ability of Cu-Co 3O4 to TMB was stable.
5) Optimizing experimental conditions
Like horseradish peroxidase (HRP), the catalytic activity of Cu-Co 3O4 NPs also depends on pH, temperature and substrate concentration. Thus, the dependence between pH, temperature, time, cu-Co 3O4 NPs concentration, H 2O2 and TMB concentration was examined. To determine the optimal reaction conditions, a series of solutions of different pH were first studied. As shown in fig. 11 (a) and (b), cu-Co 3O4 catalytically oxidizes TMB and H 2O2 at an acidic condition at a significantly faster rate than at a neutral or basic condition.
As the pH of the HAc-NaAc buffer solution increases, the absorbance value shows a trend of increasing and decreasing. At pH 4.0, the absorbance maximum was a max =1.042. Thus, the subsequent experimental selection was performed at a pH of 4.0. Fig. 11 (c) and (d) show the trend of change between temperature and catalytic activity, as can be seen from the figures. The relative activity of the reaction system had a peak at 30℃and thus the optimum temperature was determined to be 30 ℃. The effect of reaction time on enzyme activity was examined simultaneously (FIGS. 11 (e) and (f)). The relative activity shows a trend of increasing and then stabilizing along with the reaction time, and the relative activity is basically unchanged after the reaction time is prolonged to 20min, so that the reaction time is selected to be 20min in the subsequent experiment. In addition, the concentration of the catalyst Cu-Co 3O4 determines the color scale of the reaction system. Therefore, it has also been studied as an influencing factor. The relative activity is shown in FIGS. 12 (a) and (b) and is substantially unchanged when the Cu-Co 3O4 concentration is greater than 50. Mu.g/mL. Thus, the optimum catalyst concentration was determined to be 50. Mu.g/mL. Finally, the effect of TMB and H 2O2 concentrations on the catalytic activity of the enzyme was studied (FIGS. 12 (c) - (f)). Catalytic activity was maximized when TMB and H 2O2 concentrations reached 80. Mu. Mol/L and 15mM, respectively. Thus, the final optimization experimental conditions were: pH 4.0, temperature 30 ℃, reaction time 20min, cu-Co 3O4. Mu.g/mL, TMB 80. Mu. Mol/L and H 2O2 15 mM. For convenience, the subsequent experiments were all performed at room temperature (25 ℃).
6) Steady state kinetic study of Cu-Co 3O4 NPs
To further investigate the mechanism of catalytic activity of Cu-Co 3O4 NPs, studies were performed by varying the concentrations of TMB and H 2O2, and then the apparent steady state kinetic parameters were calculated according to the Miq equation. Typical mie curves (fig. 13 (a) and (c)) and corresponding double reciprocal plots (fig. 13 (b) and (d)) were obtained as a function of concentration according to lambert's law, and important enzyme kinetic parameters, such as the mie constant (K m) and the maximum initial velocity (V max), were obtained as listed in table 5.
K m is an indicator of the affinity of the enzyme for the substrate. The smaller the K m, the higher the affinity of the enzyme for the substrate. The Michaelis-Menten curve is shown in FIG. 13. Apparent steady state kinetic parameters can be obtained from the Lineweaver-Burk plot, see equation (2).
From this formula, it can be calculated that the K m and V max values of TMB are 0.07058mM and 51.55 ×10 8M·S-1.H2O2, respectively, and the K m and V max values are 17.72mM and 90.91×10 8M·S-1, respectively. Of course, a smaller value of K m indicates a stronger affinity between the enzyme and the substrate. As shown in Table 3, when TMB was the substrate, cu-Co 3O4 NPs possessed smaller K m and larger V max than HPR, mo-Co 3O4 nanotubes, co 3O4NRs、Co3O4NPs、SiO2@Co3O4 materials, demonstrating that Cu-Co 3O4 NPs have better affinity for TMB than other nanomaterials. However, the K m of Cu-Co 3O4 NPs for H 2O2 substrates was much higher than HRP. It was demonstrated that the native enzyme HRP confers a higher affinity for H 2O2. At V max, cu-Co 3O4 NPs are about 11 times that of HRP, and show stronger catalytic performance.
TABLE 3 comparison of peroxidase mimic kinetic parameters
(3) Cu-Co 3O4 NPs mimic peroxidase for detection of GSH
1) Detecting GSH selectivity
In the case of peroxidase-like catalytic reactions, most rely on the ROS produced by the decomposition of H 2O2. In this process, the substrate TMB can react with ROS, oxidized to the blue product oxTMB, and glutathione is reducing, which can reduce the blue product oxTMB to colorless TMB. Based on the above mechanism, the Cu-Co 3O4 -GSH-TMB system has great potential in detecting glutathione. Glutathione is a typical essential amino acid of the human body and plays an important role in various functional processes of cells. Therefore, the realization of sensitive detection of glutathione is of great significance.
In FIG. 14 (a), the change of the absorption spectrum of the reaction system was monitored at 652nm by adding glutathione at different concentrations with Cu-Co 3O4 NPs as catalysts and TMB and H 2O2 as substrates for a reaction time of 20 min. It was found that the absorbance gradually decreased with increasing glutathione concentration. FIG. 14 (b) shows a concentration response curve of Cu-Co 3O4 NPs for detecting glutathione content, with TMB oxidation being inhibited as the glutathione concentration increases. The color of the solution gradually becomes lighter with increasing concentration of glutathione, and finally turns colorless. When the glutathione concentration reached 100. Mu.M, the solution faded to colorless. Fig. 14 (c) shows that glutathione exhibits a good linear relationship in the range of 1-60 μm, the calibration curve is y=0.01649x+0.02366, (R 2 =0.995, n=35), the minimum detection Limit (LOD) is calculated to be about 0.53 μm (S/n=3), and the corresponding change in solution color is shown in the inset. In addition, in order to verify the selectivity of the Cu-Co 3O4 -GSH-TMB system for glutathione, several kinds of amino acids coexisting with glutathione were studied for anti-interference experiments (FIG. 14 (d)), and several kinds of amino acids were selected as tryptophan, methionine, phenylalanine, valine, histidine and threonine and the influence of metal ions common in the laboratory on the selectivity of glutathione, and the results showed that six kinds of amino acids (200. Mu.M) and other metal ions (2 mM) selected during the detection of glutathione (100. Mu.M) did not cause significant changes in the color of the reaction system, indicating that the constructed colorimetric sensing platform has excellent anti-interference ability.
In addition, the experiment also researches the catalysis mechanism and draws the corresponding catalysis mechanism graph. As shown in fig. 15.
In the first stage, after Cu-Co 3O4 NPs were added to the TMB and H 2O2 system, the color of the solution turned blue in 20min, while the absorbance at 652nm increased significantly. In the second stage, after GSH is added into oxTMB solutions, two electrons are transferred to oxTMB and oxTMB is reduced to TMB, the solution is changed from blue to colorless, and the absorbance at 652nm is reduced sharply. Meanwhile, GSH is converted to oxidized glutathione (GSSG).
2) Actual sample analysis
To explore the feasibility of the colorimetric sensor in complex biological environments, the method was applied to the detection of GSH in human serum. Because the concentration of GSH in human serum is high, the human serum is diluted first, so that the original concentration of glutathione falls within the concentration range of the standard curve measured by the experiment. Then 10.0. Mu.M, 20.0. Mu.M and 30.0. Mu.M GSH were added to the diluted serum samples, respectively, and then to the Cu-Co 3O4-H2O2 -TMB system solution. After 20min, the absorbance at 652nm was recorded. All data were repeated for three measurements and then averaged to calculate GSH content as shown in table 4. Based on the calibration curve obtained in aqueous solution (fig. 14 (d)), the original concentration of GSH in human serum samples was measured to be 3.602 μm, which is close to that measured by high performance liquid chromatography (3.453 μm). To further demonstrate the reliability of this method, the GSH content of 5 human serum samples was measured using the colorimetric sensor and HPLC, and the results are shown in Table 5. From the table, the data measured by the two methods can be well matched, and obviously, the colorimetric method can be successfully used for detecting glutathione in human serum.
To evaluate the reusability of this colorimetric method, the relative activity (%) was examined under the optimal conditions. As can be seen from fig. 16, after 5 consecutive cycles, the relative activity (%) slightly decreased from 100% to 91.8%. The result shows that the constructed Cu-Co 3O4 colorimetric sensor has the characteristics of high catalytic activity, high efficiency, good recoverability and the like.
TABLE 4 determination of glutathione in human serum
TABLE 5 determination of GSH content in different human blood samples
From the above analysis, it was found that the Cu 2+ -doped Co 3O4 octahedral nanomaterial (Cu-Co 3O4) was successfully prepared by the coprecipitation method and the calcination method. Compared with pure Co 3O4, the prepared Cu-Co 3O4 has obviously enhanced peroxidase-like activity, and can catalyze and oxidize a substrate TMB to generate a typical color reaction in the presence of H 2O2. When the doping ratio of Cu 2+ is 6.0%, the prepared Cu-Co 3O4 has better peroxidase activity. Meanwhile, a colorimetric sensor for detecting GSH is constructed and used for detecting GSH content in human serum, and the result shows that the linear range of the colorimetric sensor is 1.0-60 mu M, the lowest detection limit is 0.53 mu M, the recovery range of the standard adding recovery rate is 93.42-102.84%, a colorimetric sensing method with high sensitivity and strong selectivity is provided for detecting GSH in an actual sample, and the test platform has good development prospect in disease diagnosis and environmental monitoring.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A Cu-Co 3O4 catalyst, characterized in that the Cu-Co 3O4 catalyst is prepared using a Co-precipitation combined calcination process, and the Cu-Co 3O4 catalyst has an octahedral shape.
2. A method for preparing the Cu-Co 3O4 catalyst as claimed in claim 1, comprising the steps of:
(1) 2-5mmolCoCl 2·6H2 O and CuSO 4·5H2 O with different mole fractions are dissolved in 10mL of absolute ethyl alcohol under the magnetic stirring at 50-90 ℃, and then 40mL of ammonium oxalate solution with the concentration of 0.24mol/L is added into the mixed solution, and the mixture is stirred until a uniform pink solution is formed;
(2) After the magnetic stirring at 50-90 ℃ is continued to react for 1-6 hours, respectively washing with deionized water and ethanol for three times, filtering, and placing the sample in a vacuum drying oven at 60 ℃ for drying for 12 hours; and finally, transferring the dried sample into a crucible, and placing the crucible in a muffle furnace at 300-600 ℃ to calcine for 2-5h to obtain Cu-Co 3O4 NPs with different Cu 2+ doping ratios.
3. The method for preparing a Cu-Co 3O4 catalyst as claimed in claim 2, wherein the mole fraction of the added CuSO 4·5H2 O is 0-10%.
4. Use of the Cu-Co 3O4 catalyst according to claim 1 or the Cu-Co 3O4 catalyst prepared according to the method of claim 2 for qualitative and quantitative detection of glutathione.
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