CN112345609A - Porous hollow Co3O4Nanoprism and enzyme-free glucose sensor based thereon - Google Patents
Porous hollow Co3O4Nanoprism and enzyme-free glucose sensor based thereon Download PDFInfo
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 44
- 239000008103 glucose Substances 0.000 title claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002243 precursor Substances 0.000 claims abstract description 50
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 21
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
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- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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Abstract
The invention relates to porous Co3O4The preparation method of the nanoprism comprises the steps of enabling cobalt acetate and an ethanol solution of nitrogen-containing organic matters to react for 1-6 hours at a constant temperature of 60-70 ℃, then separating to obtain a precursor, drying the precursor, and then burning the precursor at a constant temperature of 300-500 ℃ in an air atmosphere. The nanoprism is directly used as an electrode material of the enzyme-free glucose sensor, other conductive carriers are not needed, and the electrode material shows excellent electrocatalytic oxidation performance, and has high sensitivity, low detection limit, wide linear response range, good selectivity and high stability. By using the enzyme-free glucose sensor, serum can be directly used for blood sugar detection without being diluted. The method is simple, convenient and quick to prepare, adopts cheap and easily-obtained raw materials to synthesize, is low in cost, is good in sample reproducibility, is suitable for large-scale production, and has development potential and application prospect.
Description
Technical Field
The present invention belongs toIn the field of electrochemical biosensing, in particular to porous hollow Co3O4A nanoprism, a preparation method thereof, an enzyme-free glucose sensor based on the nanoprism, a preparation method and an application thereof.
Background
Glucose detection has important applications in clinical diagnosis, food industry, biotechnology and the like, and most of electrochemical biosensors to date use enzyme-based electrodes such as glucose oxidase, horseradish peroxidase or heme as catalysts for oxidation or reduction. Among them, glucose oxidase-based biosensors are widely used due to their high sensitivity. Although glucose oxidase is more stable than other enzymes, due to the inherent instability of the enzyme molecules, biosensors based on biological components are still subject to various environmental factors such as temperature, pH, oxygen, humidity, organic reagents, toxic substances, etc., thereby affecting the sensitivity, stability and reproducibility of the sensor, possibly limiting the shelf life of the sensor system. There is therefore an urgent need to develop an inexpensive and stable enzyme-free sensor for accurately detecting glucose in blood.
Enzyme-free electrochemical biosensors have become an attractive alternative to enzyme-based electrodes due to their low cost, high stability and recyclability. A wide variety of catalysts have been explored for use in enzyme-free glucose sensors, such as carbon-based composites, noble metals (Pt, Au) and their alloys, transition metals (Cu, Ni, Mn, Co) and their oxides and hydroxides, metal alloys and bimetals, and the like. Noble metal and alloy catalysts thereof can adsorb intermediates and chlorides to cause surface poisoning, and the electrodes generally have the defects of low sensitivity, poor stability and the like and are expensive; NiO, CuO and Co3O4Isotransition metal oxides have been studied for electrochemical oxidation of glucose due to their advantages of lower cost and better biocompatibility than noble metals, among which Co3O4Is a magnetic semiconductor material, and attracts more because of simple synthesis method, high electrocatalytic activity, low cost and the likeInterest in the study. For example, Hu project group synthesizes Co using metal organic framework Materials (MOFs) as templates3O4Nanoparticles, which exhibit a relatively low detection limit (0.13. mu.M (S/N. sub.3)) and high sensitivity (520.7 mM) when used as electrodes for glucose detection-1 cm-2) And good selectivity; choi et al prepared porous Co by a one-step hydrothermal method3O4The @ graphene mesoporous spheres similarly exhibit high electrocatalytic activity in terms of glucose oxidation. Although in Co3O4Much effort has been made in the field of electrode materials, but development of rapid and simple preparation of efficient Co for use in electrochemical sensors based on glucose detection3O4Catalyst materials are still highly desirable.
Disclosure of Invention
The invention aims to provide porous hollow Co3O4A nanoprism and a preparation method thereof, and an enzyme-free glucose sensor based on the nanoprism and a preparation method and application thereof.
The technical scheme of the invention is as follows:
porous hollow Co3O4A method of making a nanoprism comprising the steps of:
(1) reacting cobalt acetate and an ethanol solution of nitrogen-containing organic matters at a constant temperature of 60-70 ℃ for 1-6 h, and then separating to obtain a cobalt-based precursor;
(2) and drying the cobalt-based precursor, and then burning at a constant temperature of 300-500 ℃ in an air atmosphere to obtain the cobalt-based precursor.
Preferably, the nitrogen-containing organic matter is thiourea, melamine, urea or L-cysteine; preferably urea.
Preferably, the molar ratio of the cobalt element in the cobalt acetate to the nitrogen element in the nitrogen-containing organic substance is 1: 10-16. Most preferably, when the nitrogen-containing organic matter in the step (1) is urea, the molar ratio of the cobalt acetate to the urea is 1: 6-8.
Preferably, the reaction temperature in step (1) is 65 ℃ and the reaction time is 4 h.
Preferably, the burning temperature in the step (2) is 350 ℃.
Preferably, the drying in the step (2) is drying at 60-80 ℃.
Preferably, the burning time in the step (2) is 1-4 h, preferably 2 h.
The invention also provides porous hollow Co prepared by the method3O4And (4) a nanoprism.
The invention also provides a porous hollow Co-based material3O4The preparation method of the nanoprism enzyme-free glucose sensor comprises the following steps:
mixing porous hollow Co3O4And adding the dispersion liquid of the nanoprism into a perfluorinated sulfonic acid solution, uniformly dispersing, coating on an Indium Tin Oxide (ITO) electrode, and drying to obtain the indium tin oxide film.
Preferably, the porous hollow Co3O4The dispersion liquid of the nanoprisms is porous hollow Co3O4Ethanol dispersion of nanoprisms.
Preferably, the mass concentration of the perfluorosulfonic acid in the perfluorosulfonic acid solution is 5%.
The invention also provides the enzyme-free glucose sensor prepared by the method.
The invention also provides application of the enzyme-free glucose sensor prepared by the method in enzyme-free glucose detection.
The invention provides a porous hollow Co-based material3O4The nanoprism enzyme-free glucose sensor has the beneficial effects that:
(1) with other porous Co3O4Compared with nano material, porous hollow Co3O4The hollow structure of the nanoprism shortens an electron transmission path, increases the contact area with electrolyte, provides more active sites and is more beneficial to the catalytic oxidation reaction of glucose.
(2) Adopts cheaper and abundant raw materials to synthesize Co3O4The nanoprism is simple to prepare, low in cost, high in yield and stability, low in requirements on reaction equipment, environment-friendly and suitable for large-scale synthesis.
(3) Co prepared by the invention3O4The electrochemical sensor constructed by the nanoprisms has a simple modification method, does not have other conductive carriers, can realize enzyme-free detection of glucose, has the advantages of high sensitivity, low detection limit, wide linear response range, good selectivity and high stability, the linear range of the enzyme-free detection of the glucose can reach 30mM, and the sensitivity is 19.83 muA mM-1 cm-2. Such a wide linear range facilitates direct detection of serum without the need for further dilution.
(4) By optimizing the molar ratio of cobalt acetate to urea, a more uniform and smooth surfaced solid prism was synthesized. And screening the calcining condition to obtain the porous hollow prism. When the amount of urea is too large or too small, a uniform hollow structure cannot be obtained under such conditions, and the collapsed structure thereof causes poor glucose oxidation performance.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a cobalt-based precursor prepared in example 1.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the cobalt-based precursor prepared in example 1.
FIG. 3 is a thermogravimetric analysis (TGA) of the cobalt-based precursor prepared in example 1.
FIG. 4 shows porous Co obtained in example 13O4X-ray powder diffraction pattern (XRD) of nanoprisms.
FIG. 5 shows porous Co obtained in example 13O4Scanning electron micrograph (a) and transmission electron micrograph (B) of the nanoprisms.
FIG. 6 shows porous Co obtained in example 13O4Amperometric response of glucose from enzyme-free glucose sensors constructed with nanoprisms.
FIG. 7 shows porous Co obtained in example 13O4An ampere response graph of stability (A) and anti-interference capability (B) of the enzyme-free glucose sensor constructed by the nanoprisms.
FIG. 8 shows the different ratios of Co-based precursors and their corresponding Co precursors obtained in examples 2, 3, 4, 53O4Scanning Electron Microscopy (SEM) of the nanomaterials (8A and B, 8D and E, 8G and H, and 8J and K are Co (OAc), respectively)2·4H2The proportion of O and urea is 2:1, 1:1, 1:8 and no precursor synthesized by urea; FIG. 8C, F, I, L are corresponding Co3O4)。
FIG. 9 shows Co obtained in examples 2, 3, 1, 4 and 53O4Cyclic voltammogram of enzyme-free glucose sensor constructed by nano material (9A, B, C, D, E are Co (OAc) respectively)2·4H2The ratio of O to urea is 2:1, 1:1, 1:6.2, 1:8, and Co obtained after calcination of a precursor synthesized by no urea3O4)。
Detailed Description
Example 1
Porous hollow Co3O4Preparing a nanoprism:
sequentially adding 1mmol of cobalt acetate and 6.2mmol of urea into 50mL of ethanol solution, carrying out solvothermal reaction at 65 ℃ for 4 hours, centrifugally cleaning with ethanol after the reaction is finished, and drying at 60 ℃ to obtain the cobalt-based precursor for later use. Calcining the precursor for 2 hours at 350 ℃ in the air atmosphere to obtain a black sample, namely the porous hollow Co3O4And (4) a nanoprism.
Example 2 (comparative example)
Porous hollow Co3O4Preparation of nanoprisms
Sequentially adding 2mmol of cobalt acetate and 1mmol of urea into 50mL of ethanol solution, carrying out solvothermal reaction for 4 hours at 65 ℃, centrifugally cleaning with ethanol after the reaction is finished, and drying at 60 ℃ to obtain the cobalt-based precursor for later use. Calcining the precursor for 2 hours at 350 ℃ in the air atmosphere to obtain a black sample, namely the porous hollow Co3O4And (4) a nanoprism.
Example 3 (comparative example)
Porous hollow Co3O4Preparation of nanoprisms
Sequentially adding 1mmol of cobalt acetate and 1mmol of urea into 50mL of ethanol solution, carrying out thermal reaction for 4 hours at 65 ℃, centrifugally cleaning with ethanol after the reaction is finished, and carrying out 60 DEG CAnd drying to obtain the cobalt-based precursor for later use. Calcining the precursor for 2 hours at 350 ℃ in the air atmosphere to obtain a black sample, namely the porous hollow Co3O4And (4) a nanoprism.
Example 4
Porous hollow Co3O4Preparation of nanoprisms
Sequentially adding 1mmol of cobalt acetate and 8mmol of urea into 50mL of ethanol solution, carrying out solvothermal reaction for 4 hours at 65 ℃, centrifugally cleaning with ethanol after the reaction is finished, and drying at 60 ℃ to obtain the cobalt-based precursor for later use. Calcining the precursor for 2 hours at 350 ℃ in the air atmosphere to obtain a black sample, namely the porous hollow Co3O4And (4) a nanoprism.
Example 5 (comparative example)
Porous hollow Co3O4Preparing a nanoprism:
adding 1mmol of cobalt acetate into 50mL of ethanol, carrying out solvothermal reaction at 65 ℃ for 4 hours, carrying out centrifugal cleaning by using ethanol after the reaction is finished, and drying at 80 ℃ to obtain a cobalt-based precursor; and (3) burning the cobalt-based precursor at a constant temperature of 350 ℃ for 2 hours in an air atmosphere to obtain the cobalt-based precursor.
Example 6
Porous hollow Co3O4Preparing a nanoprism:
adding 1mmol of cobalt acetate and 5mmol of thiourea into 50mL of ethanol, carrying out solvothermal reaction at 60 ℃ for 4 hours, carrying out centrifugal cleaning by using ethanol after the reaction is finished, and drying at 80 ℃ to obtain a cobalt-based precursor; and (3) burning the cobalt-based precursor at the constant temperature of 300 ℃ for 4 hours in the air atmosphere to obtain the cobalt-based precursor.
Example 7
Porous hollow Co3O4Preparing a nanoprism:
adding 1mmol of cobalt acetate and 2mmol of melamine into 50mL of ethanol, then carrying out solvothermal reaction for 6 hours at 70 ℃, centrifugally cleaning with ethanol after the reaction is finished, and drying at 70 ℃ to obtain a cobalt-based precursor; and (3) burning the cobalt-based precursor at a constant temperature of 500 ℃ for 1 hour in an air atmosphere to obtain the cobalt-based precursor.
Example 8
Porous hollow Co3O4Preparing a nanoprism:
adding 1mmol of cobalt acetate and 10mmol of L-cysteine into 50mL of ethanol, carrying out solvothermal reaction at 65 ℃ for 4 hours, carrying out centrifugal cleaning by using ethanol after the reaction is finished, and drying at 80 ℃ to obtain a cobalt-based precursor; and (3) burning the cobalt-based precursor at the constant temperature of 400 ℃ for 2 hours in the air atmosphere to obtain the cobalt-based precursor.
Example 9
Porous hollow Co3O4Preparing a nanoprism:
adding 1mmol of cobalt acetate and 6mmol of urea into 50mL of ethanol, carrying out solvothermal reaction at 65 ℃ for 1 hour, carrying out centrifugal cleaning by using ethanol after the reaction is finished, and drying at 80 ℃ to obtain a cobalt-based precursor; and (3) burning the cobalt-based precursor at a constant temperature of 350 ℃ for 2 hours in an air atmosphere to obtain the cobalt-based precursor.
Example 10
Porous hollow Co3O4Preparing a nanoprism:
adding 1mmol of cobalt acetate and 6.2mmol of urea into 50mL of ethanol, carrying out solvothermal reaction at 65 ℃ for 6 hours, carrying out centrifugal cleaning by using ethanol after the reaction is finished, and drying at 80 ℃ to obtain a cobalt-based precursor; and (3) burning the cobalt-based precursor at a constant temperature of 350 ℃ for 2 hours in an air atmosphere to obtain the cobalt-based precursor.
Example 11
(1) Porous Co3O4And (3) characterizing the structure and the appearance of the nanoprism:
from the SEM and TEM images of fig. 1 and 2, it can be seen that the morphology of the cobalt-based precursor was a smooth surfaced solid prism. From the TGA diagram of fig. 3, it is known that the cobalt-based precursor has a stable temperature of 300 ℃ in air. FIG. 4 is an XRD pattern of the final product obtained in example 1, which confirms that the black product obtained is Co3O4. FIG. 5 shows Co3O4From which it can be seen that the surface becomes rough and many pores are formed but the morphological size remains substantially unchanged, and TEM further confirms Co3O4Is a porous hollow prism.
The porous hollow structure shortens an electron transmission path, increases the contact area with electrolyte, provides more active sites and is more beneficial to the catalytic oxidation reaction of glucose.
(2) Porous Co3O4Preparing a non-enzyme glucose sensor constructed by a nanoprism:
porous hollow Co obtained in example 13O4And adding the nanoprism into ethanol to prepare a dispersion liquid, then adding the dispersion liquid into a 5% perfluorosulfonic acid solution, uniformly dispersing, coating on an indium tin oxide electrode (ITO), and drying to obtain the indium tin oxide electrode.
Corresponding performance tests of the constructed enzyme-free glucose sensor:
the detection experiment is to use a CHI 660D electrochemical workstation to carry out electrochemical test analysis by constructing a standard three-electrode system, wherein the three-electrode system comprises the following components in parts by weight: and (3) taking a platinum electrode as a counter electrode, taking the enzyme-free glucose sensor prepared in the step (2) as a working electrode, and taking a saturated calomel electrode as a reference electrode (SCE). As shown in FIG. 6, under optimized conditions, 0.05M NaOH is used as electrolyte solution, glucose with different concentrations is added under the voltage of 0.6V to obtain the linear range (up to 30mM) of the glucose sensor, the wider linear range can be used for directly detecting the glucose concentration in serum, the blood does not need to be diluted, and the sensitivity is 19.83 muA mM-1 cm-2The detection limit was 28.6. mu.M. Meanwhile, stability test of the sensor is also carried out, and as can be seen from fig. 7A, after the electrode is placed for 25 days, the current response can still keep 95.3% of the initial response, which effectively indicates that the glucose sensor has excellent stability, probably due to the porous Co3O4The high stability inherent to nanoprisms. In addition, a plurality of substances are selected for anti-interference test: glycine (Gly), Ascorbic Acid (AA), fructose (Fru), Uric Acid (UA) and L-cysteine (Lcy). As shown in FIG. 7B, after the interfering substance is added, the response current is almost small, which indicates that the glucose sensor has strong anti-interference capability.
Example 12: comparative example
(1) Common Co3O4Preparation of nanomaterials：
1mmol of Co (OAc)2·4H2And adding O into 50mL of ethanol solution, carrying out solvothermal reaction for 4 hours at 65 ℃, carrying out centrifugal cleaning by using ethanol after the reaction is finished, and drying at 60 ℃ to obtain the cobalt-based precursor for later use. Calcining the precursor at 350 ℃ for 2 hours in the air atmosphere to obtain a black sample, namely cobaltosic oxide (Co)3O4)。(2)Co3O4Morphology characterization of nanomaterials
FIG. 8 shows the precursor synthesized from cobalt acetate and urea in different ratios and common Co3O4SEM image of (d). Wherein FIGS. 8A and B, 8D and E, 8G and H, and 8J and K are Co (OAc), respectively2·4H2The SEM images of the precursors synthesized by the urea in the proportion of 2:1, 1:1 and 1:8 are shown, and the larger the added amount of the urea is, the larger the size of the precursor is, the more regular the precursor is, and the smoother the surface is. FIG. 8C, F, I, L are corresponding Co3O4The SEM image shows that Co is obtained under the same calcination conditions and under urea-free conditions3O4The original morphology cannot be maintained by the substantial formation of particles.
(3)Co3O4Constructing a non-enzyme glucose sensor by using the nano material and testing the corresponding performance of the sensor:
in the detection experiment, a CHI 660D electrochemical workstation is also utilized to carry out electrochemical test analysis by constructing a standard three-electrode system, wherein the three-electrode system comprises the following components: co prepared on the basis of examples 2, 3, 4, 5 with a platinum electrode as counter electrode3O4The nanomaterial was used as the working electrode (prepared as in example 11) and the saturated calomel electrode was used as the reference electrode (SCE). FIGS. 9A, B, C, D, E are Co (OAc) with 1mM glucose added2·4H2The ratio of O to urea is 2:1, 1:1, 1:6.2, 1:8 and Co synthesized without urea3O4According to the cyclic voltammogram of the nano material, the amount of urea is increased, the response current is increased, but after the amount of urea is increased to 8mmol, the response current is obviously reduced, the performance of the nano particle is far lower than that of a porous hollow structure, the superiority of the porous hollow structure is further illustrated, and the cyclic voltammogram can effectively improveHigh glucose electrocatalytic performance.
The enzyme-free glucose sensor constructed by the electrode material shows a wider linear range (up to 30mM), is easy to directly detect the glucose concentration in serum, and does not need to be diluted. The electrode material is simple to prepare, low in raw material cost, rich in resources, capable of being synthesized in a large scale, free of other carriers and capable of displaying high electrocatalytic oxidation performance.
Claims (10)
1. Porous Co3O4The preparation method of the nanoprism is characterized by comprising the following steps:
(1) reacting cobalt acetate and an ethanol solution of nitrogen-containing organic matters at a constant temperature of 60-70 ℃ for 1-6 h, and then separating to obtain a cobalt-based precursor;
(2) and drying the cobalt-based precursor, and then burning at a constant temperature of 300-500 ℃ in an air atmosphere, preferably 350 ℃, so as to obtain the cobalt-based precursor.
2. The method according to claim 1, wherein the nitrogen-containing organic compound is thiourea, melamine, urea or L-cysteine; preferably, the nitrogen-containing organic substance is urea.
3. The method according to claim 1, wherein the reaction temperature in the step (1) is 65 ℃ and the reaction time is 4 hours.
4. The preparation method according to claim 1, wherein the molar ratio of cobalt element in the cobalt acetate to nitrogen element in the nitrogen-containing organic substance in step (1) is 1: 10-16.
5. The preparation method according to claim 1, wherein the drying in step (2) is drying at 60-80 ℃.
6. The preparation method according to claim 1, wherein the burning time in the step (2) is 1-4 h; preferably for 2 hours.
7. Porous hollow Co prepared by the preparation method of any one of claims 1 to 63O4And (4) a nanoprism.
8. Porous hollow Co prepared based on preparation method of any one of claims 1-63O4The preparation method of the nanoprism enzyme-free glucose sensor is characterized by comprising the following steps of:
mixing the porous Co3O4And adding the dispersion liquid of the nanoprism into a perfluorinated sulfonic acid solution, uniformly dispersing, coating on an indium tin oxide electrode, and drying to obtain the indium tin oxide electrode.
9. The enzyme-free glucose sensor prepared by the method of claim 8.
10. Use of the enzyme-free glucose sensor prepared by the method of claim 8 for the enzyme-free detection of glucose.
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| CN102849804A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Cobaltosic oxide columnar structure material and preparation method thereof |
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| CN102849804A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Cobaltosic oxide columnar structure material and preparation method thereof |
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