CN105606672A - Preparation method and application of nano-scale hollow spherical metallic oxide material - Google Patents
Preparation method and application of nano-scale hollow spherical metallic oxide material Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a nano-scale hollow spherical metallic oxide material. The preparation method comprises the following steps: at room temperature, compounding 2-methylimidazole and cobalt acetate into a zeolite imidazole framework structure (ZIFs) material; putting the ZIFs material into a porcelain boat; at temperature higher than decomposing temperature of organic ligand of the ZIFs material, calcining the material in a muffle furnace and then cooling to room temperature; taking out the material, thereby acquiring a product applied to electrochemical detection. A sensor is high in sensitivity, low in limit of detection, wide in detection scope and fast in response and has huge application potential at the aspect of electrochemical sensing. Compared with a traditional method, the preparation method provided by the invention has the advantages that the method is simple, no rigor condition is required in a compounding process, energy is saved and no pollution is generated; the applied composing materials are all low in cost and easily available, thereby facilitating industrial production and preparation; the composing with the size and shape of metallic oxide controllable is beneficial to effective application of the metallic oxide at the electro-catalysis aspect.
Description
Technical field
The present invention relates to inorganic chemistry, organic chemistry and materials chemistry crossing domain, particularly a kind of nanoscaleThe preparation method of hollow ball-shape metal oxide materials and application are a kind of application in electrochemical sensing.
Background technology
The detection of hydrogen peroxide all plays an important role at food, chemistry, biology, clinical diagnosis and field of environment protection. To orderBefore till, multiple detection means all obtains extensively as chemoluminescence method, electrical analysis, spectrum, chromatogram etc. in the detection of hydrogen peroxideGeneral application. Wherein electrochemical method, due to the advantage such as easy and simple to handle, sensitivity is high, enjoys the concern of researcher. In the pastIn research, because enzyme is higher to the specificity of analyte, therefore the bibliographical information of studying enzyme sensor is also more. But enzyme toolHave the shortcoming of self, that is: be difficult for preservation, expensive, purification more complicated, these intrinsic shortcomings have directly limited enzyme at electricityUse in chemical sensitisation. In view of this, non-enzyme electrochemical sensor also more and more carrys out to be more subject to the attention of researcher, eachPlant functional material, as noble metal, CNT, metal oxide etc., be all widely applied to sending out in research of non-enzyme sensorBut compared with enzyme sensor, the sensitivity of non-enzyme sensor and selectively poor. Co3O4As transition metal oxideOne can play catalytic action, based on Co in the detection of hydrogen peroxide3O4The hydrogen peroxide electrochemical sensor crowd that is also in the newsInstitute is known, Co3O4The factor such as size, pattern, specific surface can affect its catalytic performance, therefore by suitable synthetic sideMethod, obtains the Co of different-shape3O4Nano material, can improve based on Co3O4The sensitivities of electrochemical sensor to hydrogen peroxideEnergy.
Preparation Co at present3O4The method of nanostructured has following several, as solid-state reaction (BaydiM.E., PoilleratG.,RehspringerJ.-L.,Gautier,J.L.,Koenig,J.-F.,ChartierP.JournalofSolidStateChemistry, 1994,109,281-288.), spray pyrolysis (FujiiE., ToriiH.,TomozawaA.,TakayamaR.,HiraoT.Journalofmaterialsscience,1995,30,6013-6018.), chemical vapour deposition (CVD) (GautierJ.L., RiosE., GraciaM., MarcoJ.F.,GancedoJ.R.ThinSolidFilms, 1997,311,51-57.) and sol-gel synthesis route (SakamotoS.,YoshinakaM.,HirotaK.,YamaguchiO.JournaloftheAmericanCeramicSociety, 1997,80,267-268.). Zeolite imidazoles frame structure material (ZIFs) is that a class is taking organic imidazoles as connectionThe nitrogen heterocyclic ring metal-organic framework materials (MOFs) of part, ZIFs is except having specific area that conventional MOFs material is larger and manyOutside pore property, due to the strong interaction between imidazoles chain and metal ion, such material also have higher heat endurance andChemical stability, make its gas storage with separate, catalysis, chemical sensitisation with film separates etc. aspect shown good shouldUse prospect. The spies such as the porous of ZIFs material, bigger serface, controlled skeleton structure and high density scattered metal positionPoint, making using ZIFs as presoma preparation have highly active nano-metal-oxide becomes a kind of effectively preparation sideMethod.
Summary of the invention
Object of the present invention is exactly in view of the foregoing defects the prior art has, and a kind of nanoscale hollow ball-shape gold is providedBelong to preparation method and the application of oxide material, by the zeolite imidazoles frame structure material (ZIFs) to contain this metal as frontDrive body, under specified temp to ZIFs calcined material, controlled synthetic different-shape, the metal oxide of size, and willIt is applied to Electrochemical Detection hydrogen peroxide, and this sensor sheet reveals high sensitivity, low detectability, wide detection range and fast soundBetween seasonable, aspect electrochemical sensing, there is very large potentiality application.
The preparation method of a kind of nanoscale hollow ball-shape metal oxide materials that the present invention mentions, preparation method asUnder:
(1), at room temperature, soluble in water respectively by glyoxal ethyline and cobalt acetate, and by magnetic stirrer, then willTwo solution mix and blends, gained precipitation washes with water and is centrifugal, reject supernatant, repeatedly, 60 is Celsius for repeated washing centrifugally operatedDegree is dried, thereby obtains synthetic zeolite imidazoles frame structure material ZIFs;
(2), zeolite imidazoles frame structure material ZIFs is carried out to thermogravimetric test, material is placed in to porcelain boat, higher than ZIFs materialUnder material organic ligand decomposition temperature, in Muffle furnace, to calcined material, calcination temperature range is between 500-800 DEG C, and speed heats upRate is 2 DEG C/min; Be cooled to again room temperature, take out material, obtain described nano-scale hollow ball-shape metal oxide Co3O4。
Above-mentioned zeolite imidazoles frame structure material ZIFs is ZIF-67.
The nano-scale hollow ball-shape metal oxide Co that the present invention is prepared3O4Application, be applied to electrochemical sensingDevice, by by modified metal oxide in working electrode surface, in alkaline solution, detect and add and do not add thing to be detectedThe variation of current signal, thus play the effect that detects this material, and detection thing is hydrogen peroxide.
The nano-scale hollow ball-shape metal oxide Co that the present invention is prepared3O4Application, its electrochemical detection method asUnder:
(1), metal oxide materials is modified in working electrode surface, in alkaline solution, hydrogen peroxide being carried out to cyclic voltammetric ringsShould;
(2), metal oxide materials is modified in working electrode surface, under constant potential, in alkaline solution, hydrogen peroxide is enteredThe response of row ampere;
(3), metal oxide materials is modified in working electrode surface, under constant potential in alkaline solution to modified electrodeCarry out stability test;
(4), metal oxide materials is modified in working electrode surface, under constant potential, in alkaline solution, disturb surveyExamination;
Described metal oxide is nano-scale hollow ball-shape metal oxide Co3O4, working electrode is glass-carbon electrode, alkalescence is moltenLiquid is the NaOH aqueous solution.
The invention has the beneficial effects as follows: compared with conventional method, the present invention also has advantages of following outstanding: 1, method letterSingle, in building-up process, without harsh conditions, save the energy, pollution-free; 2, synthetic material used is all cheap and easy to get, is beneficial to industrializationManufacture; 3, the size to metal oxide, pattern controlledly synthesis, is conducive to metal oxide more having aspect electro-catalysisThe application of effect. The method aspect the various nano-metal-oxides of preparation, application aspect and the electrochemistry of expansion ZIFs materialSensor field has great importance and application prospect widely.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph (SEM) of the ZIF-67 nano material prepared of embodiment 1;
Fig. 2 is Co prepared by embodiment 23O4Powder x-ray diffraction collection of illustrative plates (XRD), the SEM of nano material are shoneSheet (SEM) and transmission electron microscope photo (TEM);
Fig. 3 is under embodiment 3 unmodified electrodes and modified electrode, respectively the circulation after not adding hydrogen peroxide and adding hydrogen peroxideVolt-ampere curve;
Fig. 4 is under embodiment 4 modified electrodes, constantly adds ampere response curve that the hydrogen peroxide of variable concentrations obtains, adds oneDetermine the stability response curve after concentration hydrogen peroxide and add the ampere response curve after chaff interference.
Detailed description of the invention
Set forth technical characterstic of the present invention below in conjunction with specific experiment scheme and accompanying drawing, but the present invention is not limited thereto.Test method described in embodiment below, if no special instructions, is conventional method; Described instrument and material, if no special instructions,All can obtain from existing market approach.
Embodiment 1: the synthetic method of zeolite imidazoles frame structure material ZIF-67 is as follows: under room temperature, by 1.3686gmIm(glyoxal ethyline) and 0.4152g cobalt acetate are dissolved in respectively in 15ml water, on the magnetic stirring apparatus of 800r/min, stir 30Minute, then by two solution mix and blend 10 minutes, gained precipitation washes with water and is centrifugal, reject supernatant. Repeated washing fromHeart operation 3 times, dries 10 hours for 60 degrees Celsius. Sample is carried out to SEM sign, as shown in the figure, can find out the ZIF-of synthesized67 materials are the subsphaeroidal particle of average grain diameter 400nm left and right.
Nano-metal-oxide Co3O4Synthetic method: the ZIF-67 product obtaining is put in porcelain boat, is placed in Muffle furnaceIn, 2 ° of C/min of heating rate, are raised to 700 degrees Celsius of constant temperature 1 hour, finally drop to room temperature and take out product. Sample is carried out to XRDCharacterize, as shown in the figure, can find out obtained product and Co3O4Standard x RD spectrogram (YuDing, YingWang, LiangSu,MichaelBellagamba,HengZhang,YuLei,BiosensorsandBioelectronics,2010,26,542-548) coincide, show sample better crystallinity degree, sample is pure. Get sample segment, it carried out to SEM sign,Can find out gained Co3O4Material is the particle of average grain diameter 230nm left and right, and has kept the subsphaeroidal pattern of ZIF-67 material.Get sample segment, it is carried out to TEM sign, can see gained Co3O4Material has porous.
Embodiment 2: difference from Example 1 is: at nano-metal-oxide Co3O4Synthetic method in, by what obtainZIF-67 product is put in porcelain boat, is placed in Muffle furnace, and 2 ° of C/min of heating rate, are raised to 800 degrees Celsius of constant temperature 1 hour,After drop to room temperature take out product.
Embodiment 3: difference from Example 1 is: at nano-metal-oxide Co3O4Synthetic method in, by what obtainZIF-67 product is put in porcelain boat, is placed in Muffle furnace, and 2 ° of C/min of heating rate, are raised to 500 degrees Celsius of constant temperature 1 hour,After drop to room temperature take out product.
In addition, the nano-metal-oxide Co that the present invention obtains3O4, taking embodiment 1 as example, be applied to Electrochemical DetectionMethod is as follows:
(a) the catalytic oxidation process of hydrogen peroxide: employing glass-carbon electrode is working electrode, platinum filament is to electrode, silver-colored silver chlorate referenceElectrode. On polishing cloth, with the alumina particle polishing glass-carbon electrode of 0.05 μ m, then use respectively ethanol and deionized water ultrasonic5min, in air drying. 2.0mgCo3O4In 1ml deionized water for ultrasonic 30min become suspension, get 10 μ L drip inGlass-carbon electrode surface, in air drying 40min, makes modified electrode. The electrode of unmodified and modification is placed in respectively to 0.1In MNaOH solution, carry out cyclic voltammetric response not adding and add under 10mM hydrogen peroxide respectively, sweep speed is 100MV/s, scanning voltage 0-0.7V. Can find out from the cyclic voltammetry curve obtaining, naked glass-carbon electrode is adding 10mM dioxygenVolt-ampere curve before and after water does not have significant change, shows that the chemical reaction of hydrogen peroxide on naked glass-carbon electrode is very limited, and Co3O4Nano particle has good electro catalytic activity to hydrogen peroxide, causes Co3O4Nano-particle modified glass-carbon electrode add hydrogen peroxide withRear oxidation peak current obviously strengthens. Therefore, this electrode can be used as the electrochemical sensor that detects hydrogen peroxide.
(b) the constant potential ampere testing process of hydrogen peroxide and disturbed test process: in constant potential 0.39V, sweep speedUnder the operating condition of 100mV/s, Co3O4Nano-particle modified glass-carbon electrode constantly adds dioxygen in the 0.1MNaOH aqueous solutionM-current-responsive test (this experiment under agitation completes always) when water quality standard sample carries out. To Co3O4Nano-particle modifiedGlass-carbon electrode carries out stability test, under 0.39V constant potential, adds 0.1mM hydrogen peroxide in 0.1MNaOH solution, ringsAnswer 30min. Under 0.39V, hydrogen peroxide is carried out to disturbed test equally, add respectively 0.2mM second alcohol and glucose as dryDisturb thing, m-current-responsive test while carrying out. Obtain ampere a response curve show, this sensor is very fast to the response of hydrogen peroxide,Large 95% the steady-state current that reaches in 3s; Detection range is between 0.4 μ m-2.2mM; This sensor pair calculatingThe sensitivity of hydrogen peroxide is 120.55 μ A/mM(S/N=3), detect and be limited to 0.24 μ m. The figure that stability test obtains shows,In 30min, response current does not decline substantially, shows that the sensor of preparation has good stability. Disturbed test obtainsAmpere a response curve show, this sensor does not respond second alcohol and glucose, and Co is described3O4Nano-particle modified electrodeHydrogen peroxide is had well selective.
In sum, the present invention is taking zeolite imidazoles frame structure material ZIFs as predecessor, by by it in uniform temperatureLower calcining, has obtained the hollow ball-shape metal oxide of nano-scale, has confirmed its structure by powder x-ray diffraction analysisWith the uniformity of reference material, characterize its size and pattern by SEM and transmission electron microscope, product is pureOnly, degree of crystallinity is high. Synthetic nano-metal-oxide is modified in electrode surface, hydrogen peroxide is carried out to catalytic oxidation test,Show high sensitivity, low detectability, wide detection range, fast-response time, and there is good stability and selective,There is important value in the application in chemical sensor field.
In addition, embodiments of the invention are mainly described preparation method and application in detail as an example of ZIF-67 example, certainly, and zeoliteImidazoles frame structure material ZIFs can be also ZIF-9(central ion: cobalt; Part: bIm, bibliography: K.Park, Z.Ni,A.C?té,J.Choi,R.Huang,F.Uribe-Romo,H.Chae,M.O’Keeffe,O.Yaghi, Prov.Natl.Acad.Sci.U.S.A., 2006,103,10186-10191), ZIF-69(centerIon: zinc; Part: cBIm and nIm, bibliography: R.Banerjee, A.Phan, B.Wang,C.Knobler,H.Furukawa,M.O’Keeffe,O.Yaghi,Science,2008,319,939-943), ZIF-90(central ion: zinc; Part: Ica, bibliography: W.Morris, C.Doonan, H.Furukawa,R.Banerjee,O.Yaghi,J.Am.Chem.Soc.,2008,130,12626-12627)、HKUST-1(central ion: Cu; Part: BTC, bibliography: J.L.Zhuang, D.Ceglarek, S.Pethuraj,A.Terfort) all can be by synthetic its corresponding metal oxide of similar approach.
The above, be only part preferred embodiment of the present invention, and any those of ordinary skill in the art all may profitWith the technical scheme correct of above-mentioned elaboration or be revised as the technical scheme being equal to. Therefore, according to technology of the present inventionAny simple modification that scheme is carried out or be equal to displacement, belongs to the greatest extent the scope of protection of present invention.
Claims (4)
1. a preparation method for nanoscale hollow ball-shape metal oxide materials, is characterized in that preparation method is as follows:
(1), at room temperature, soluble in water respectively by glyoxal ethyline and cobalt acetate, and by magnetic stirrer, then willTwo solution mix and blends, gained precipitation washes with water and is centrifugal, reject supernatant, repeatedly, 60 is Celsius for repeated washing centrifugally operatedDegree is dried, thereby obtains synthetic zeolite imidazoles frame structure material ZIFs;
(2), zeolite imidazoles frame structure material ZIFs is carried out to thermogravimetric test, material is placed in to porcelain boat, higher than ZIFs materialUnder material organic ligand decomposition temperature, in Muffle furnace, to calcined material, calcination temperature range is between 500-800 DEG C, and speed heats upRate is 2 DEG C/min; Be cooled to again room temperature, take out material, obtain described nano-scale hollow ball-shape metal oxide Co3O4。
2. the preparation method of nanoscale hollow ball-shape metal oxide materials according to claim 1, is characterized in that: instituteThe zeolite imidazoles frame structure material ZIFs stating is ZIF-67.
3. a nano-scale hollow ball-shape metal oxide Co as prepared in claim 1 or 23O4Application, its featureBe: be applied to electrochemical sensor, by by modified metal oxide in working electrode surface, in alkaline solution, detect and addDo not add the variation of the current signal of thing to be detected, thereby play the effect that detects this material, detection thing is hydrogen peroxide.
4. according to the prepared nano-scale hollow ball-shape metal oxide Co of claim 33O4Application, it is characterized in that electrificationDetection method is as follows:
(1), metal oxide materials is modified in working electrode surface, in alkaline solution, hydrogen peroxide being carried out to cyclic voltammetric ringsShould;
(2), metal oxide materials is modified in working electrode surface, under constant potential, in alkaline solution, hydrogen peroxide is enteredThe response of row ampere;
(3), metal oxide materials is modified in working electrode surface, under constant potential in alkaline solution to modified electrodeCarry out stability test;
(4), metal oxide materials is modified in working electrode surface, under constant potential, in alkaline solution, disturb surveyExamination;
Described metal oxide is nano-scale hollow ball-shape metal oxide Co3O4, working electrode is glass-carbon electrode, alkalescence is moltenLiquid is the NaOH aqueous solution.
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Cited By (9)
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| CN107516741A (en) * | 2017-06-28 | 2017-12-26 | 浙江工业大学 | A kind of N of the metal Co loads with excellent electrocatalytic oxidation reducing property adulterates the synthetic method of three-dimensional porous carbon material |
| CN108598471A (en) * | 2018-05-21 | 2018-09-28 | 武汉理工大学 | A kind of sodium-ion battery positive electrode containing cobalt and preparation method thereof |
| CN109589979A (en) * | 2017-09-30 | 2019-04-09 | 黑龙江大学 | A kind of metal oxide/carbon material compound and its preparation method and application |
| CN109603914A (en) * | 2019-01-16 | 2019-04-12 | 济南大学 | A method of etching prepares hollow HKUST-1/ZIF-67 composite nanoparticle |
| CN109824093A (en) * | 2019-04-12 | 2019-05-31 | 武夷学院 | A kind of Co being layered porous hollow core-shell structure3O4High-efficiency synthesis method |
| CN110156092A (en) * | 2018-11-12 | 2019-08-23 | 淮阴师范学院 | A kind of dried persimmon shape cobaltosic oxide lithium cell cathode material and preparation method thereof |
| CN111185242A (en) * | 2020-01-09 | 2020-05-22 | 五邑大学 | Co3O4-mMOxZIFs composite material and preparation and application thereof |
| US10889598B2 (en) * | 2017-11-21 | 2021-01-12 | Wisconsin Alumni Research Foundation | Method to make scalable ultrathin hexagonally faceted metal-organic framework (MOF) and method of using same for detecting explosives and other nitro-aromatic compounds |
| CN115112728A (en) * | 2022-06-30 | 2022-09-27 | 国纳纳米技术研究(河北)有限公司 | Preparation method of high-sensitivity electrochemical sensor for detecting hydrogen peroxide, product and application thereof |
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| CN107516741B (en) * | 2017-06-28 | 2020-03-17 | 浙江工业大学 | Synthesis method of metal Co-loaded N-doped three-dimensional porous carbon material with excellent electrocatalytic oxygen reduction performance |
| CN107516741A (en) * | 2017-06-28 | 2017-12-26 | 浙江工业大学 | A kind of N of the metal Co loads with excellent electrocatalytic oxidation reducing property adulterates the synthetic method of three-dimensional porous carbon material |
| CN109589979A (en) * | 2017-09-30 | 2019-04-09 | 黑龙江大学 | A kind of metal oxide/carbon material compound and its preparation method and application |
| US10889598B2 (en) * | 2017-11-21 | 2021-01-12 | Wisconsin Alumni Research Foundation | Method to make scalable ultrathin hexagonally faceted metal-organic framework (MOF) and method of using same for detecting explosives and other nitro-aromatic compounds |
| US11661432B2 (en) | 2017-11-21 | 2023-05-30 | Wisconsin Alumni Research Foundation | Method to make scalable ultrathin hexagonally faceted metal-organic framework (MOF) and method of using same for detecting explosives and other nitro-aromatic compounds |
| CN108598471B (en) * | 2018-05-21 | 2020-11-20 | 武汉理工大学 | Cobalt-containing positive electrode material of sodium ion battery and preparation method thereof |
| CN108598471A (en) * | 2018-05-21 | 2018-09-28 | 武汉理工大学 | A kind of sodium-ion battery positive electrode containing cobalt and preparation method thereof |
| CN110156092A (en) * | 2018-11-12 | 2019-08-23 | 淮阴师范学院 | A kind of dried persimmon shape cobaltosic oxide lithium cell cathode material and preparation method thereof |
| CN109603914A (en) * | 2019-01-16 | 2019-04-12 | 济南大学 | A method of etching prepares hollow HKUST-1/ZIF-67 composite nanoparticle |
| CN109824093A (en) * | 2019-04-12 | 2019-05-31 | 武夷学院 | A kind of Co being layered porous hollow core-shell structure3O4High-efficiency synthesis method |
| CN111185242A (en) * | 2020-01-09 | 2020-05-22 | 五邑大学 | Co3O4-mMOxZIFs composite material and preparation and application thereof |
| CN111185242B (en) * | 2020-01-09 | 2022-12-13 | 五邑大学 | Co 3 O 4 -mMO x ZIFs composite material and preparation and application thereof |
| CN115112728A (en) * | 2022-06-30 | 2022-09-27 | 国纳纳米技术研究(河北)有限公司 | Preparation method of high-sensitivity electrochemical sensor for detecting hydrogen peroxide, product and application thereof |
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