CN110128673B - Cerium-based metal organic framework for Cr (VI) detection, preparation method and application - Google Patents
Cerium-based metal organic framework for Cr (VI) detection, preparation method and application Download PDFInfo
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Abstract
The invention relates to the technical field of optical sensing, and particularly discloses a cerium-based metal organic framework for Cr (VI) detection, a preparation method and application thereof. The cerium-based metal organic framework takes cerium dioxide nanorods with simulated enzyme activity as templates, cerium ions are provided as ion centers, terephthalic acid is added, and the cerium-based metal organic framework grows through nucleation. The cerium dioxide nanorod is obtained by mixing and reacting cerous nitrate hexahydrate and sodium hydroxide, centrifuging, washing and drying in vacuum, and the cerium-based metal organic framework is applied to detecting Cr (VI). The invention synthesizes the cerium-based metal organic framework with specific CeO by using a sacrificial template method for the first time2The nano material has stronger oxidase activity and selectivity, realizes the sensitive detection of Cr (VI), has the advantages of high sensitivity, good selectivity, simplicity and quickness, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of optical sensing, and particularly relates to a cerium-based metal organic framework for Cr (VI) detection, a preparation method and application thereof.
Background
Chromium is the 21 st element in the crust and is present in the environment in mainly two oxidation states cr (iii) and cr (vi). Metal plating and processing, leather tanning, preservation of industrial cooling water, and wood preservation treatments, among others, can all result in elevated chromium concentrations in the environment. The two oxidation states of Cr have significantly different chemical properties and human toxicity. Cr (iii) is a trace element required by the human body, is less toxic, and can form trivalent cations (or hydrolysates), strongly bind to mineral surfaces and form metal hydroxides with limited solubility. While cr (vi) is known as a human respiratory carcinogen, usually as a chromate oxyanion, in addition to carcinogenesis, some cr (vi) -containing compounds have been found to be powerful epithelial irritants and nervous tissue degradation factors, while also tending to migrate in the environment, thereby compromising water quality. The world health organization in the Drinking Water quality guidelines (fourth edition) specifies that the maximum contamination level of total chromium in water is 50 μ g/L. Therefore, monitoring, accurate identification and quantitative detection of Cr (VI) are important. Up to now, there are few methods for direct detection of cr (vi) in aqueous environments, except for traditional analytical methods such as mass spectrometry, electrochemistry, chromatography and fluorescence spectroscopy. Moreover, these methods usually require long and complicated operations, and are not suitable for the rapid and efficient determination of Cr (VI). In recent years, emerging colorimetric strategies based on nanoenzyme materials have wide application in water pollutant detection due to the stability of detection and the capability of resisting complex medium interference.
The cerium oxide nano material has excellent physicochemical properties such as high oxygen vacancy, defect and double oxidation state, and can effectively adsorb and remove Cr (VI) (Mishra, P.K.; Kumar, R.; Rai, P.K. surfactant-free one-dot synthesis CeO)2,TiO2and Ti @ Ce oxide nanoparticles for the ultra fast removal of Cr (VI) from aqueous medium, 2018,10(15), 7257-7269. Furthermore, the low solubility and low toxicity of cerium oxide nanomaterials in acidic media makes them more attractive than other metal oxides for water remediation. The nano enzyme is one of emerging nano materials, has higher stability and lower cost than natural enzyme, and is widely applied to biosensors and nano medicine. Cerium oxide has excellent nanoenzyme activity due to the presence of two oxidation states and a large number of oxygen vacancies (Cao, f.; Zhang, y.; Sun, y.; Wang, z.; Zhang, l.; Huang, y.; Liu c.; Liu, z.; Ren, j.; Qu, x.ultrasmall microorganisms isolated with in pore carbon sources frames for synthetic peptide therapeutics: enhanced oxidative and reduced energy analysis chemistry of Materials,2018,30(21), 7831-.
Metal Organic Framework (MOF) materials are currently a focus of research, and based on the use of MOFs for loading functional materials, the development of new types of platforms is of interest. Compared to MOFs, heterostructures of MOFs in combination with other functional materials show great advantages due to synergistic effects. The sacrificial template method was originally developed from the natural phenomenon of Pseudomorphic minor replacement (i.e., transformation of an unbalanced mineral phase into a thermodynamically more stable phase involving dissolution and reprecipitation, dissolution kinetics combined with nucleation and crystallization kinetics of new phases preserving the shape and size of the parent phase being replaced) by the Kitagawa project group in 2012 to construct alumina-templated porous coordination polymers, organic substances combined with preformed metal oxide precursors, porous coordination polymerization being formed on a molecular scale by the Pseudomorphic minor replacement simultaneously with the retention of the precursors (Reboul, J.; Furukawa, S.H.; Horike, N.Tsotsaras, M.; Hirai, K.; Uehara, H.; Kondo 2012, M.; Louvain, N.; O.; custom porous ceramic, S.coli, 717 reaction, Nature reaction, 11). In 2017, the Lu topic group applied a sacrificial template method to synthesize various metal-organic frameworks using metal oxides as templates, and adjusted the spatial distribution of metal-composited metal nanoparticles in MOFs by changing the concentration of organic ligands to improve the catalytic efficiency (Yang, Q.; Liu, W.; Wang, B.; Zhang, W.; Zeng, X.; Zhang, C.; Qin, Y.; Sun, X.; Wu, T.; Liu J.; Huo, F.; Lu, J.Regulation and specific distribution of metal nanoparticles with metal-organic framework catalytic synthesis carbon interactions, 2017,8, 14429). In the sacrificial template approach, the metal oxide template can provide metal ions by sacrificing itself, and then initiate the growth of MOFs without any surface modification.
A novel colorimetric method for Cr (VI) detection is constructed by synthesizing a cerium-based metal organic framework by using a sacrificial template method and combining the oxidase activity of the cerium-based metal organic framework with a novel Cr (VI) -TMB system, and related reports are not found yet.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects and shortcomings of the existing Cr (VI) detection method, a cerium-based metal organic framework for Cr (VI) detection, a preparation method and a product thereofApplication is carried out. The invention synthesizes the cerium-based metal organic framework with specific CeO by using a sacrificial template method for the first time2The nano material has stronger oxidase activity and selectivity, realizes the sensitive detection of Cr (VI), has the advantages of high sensitivity, good selectivity, simplicity and quickness, and has good application prospect.
The principle of the invention is as follows:
with cerium dioxide nanorods (CeO) with mimic enzymatic activity2NRs) providing cerium ion as ion center for template, adding terephthalic acid to initiate cerium-based metal organic framework (CeO)2NRs-MOF) and also retains CeO2Morphology and properties of NRs. CeO formed based on sacrificial template method2NRs-MOF to CeO2The nano material has stronger oxidase activity and selectivity without H2O2In the presence of Cr (VI) instead of H2O2And forming a Cr (VI) -TMB new system with TMB, oxidizing the TMB for color development, wherein the ultraviolet absorption peak of the TMB at 650nm is increased along with the increase of the concentration of Cr (VI), and accordingly, constructing a simple and sensitive colorimetric method for the oxidase activity based on the cerium-based metal organic framework, and being used for quantitative analysis and adsorption research of Cr (VI) in environmental samples.
The invention adopts the following technical scheme to achieve the purpose of the invention.
First, the present invention provides a cerium-based metal organic framework for cr (vi) detection.
The cerium-based metal organic framework is formed by cerium dioxide nanorods (CeO) with simulated enzyme activity2NRs) as template, providing cerium ion as ion center, adding terephthalic acid, nucleating and growing to obtain cerium-based metal organic framework (CeO)2NRs-MOF)。
Further, the cerium dioxide nanorods (CeO)2NRs) are prepared by mixing and reacting cerous nitrate hexahydrate and sodium hydroxide, centrifuging, washing and drying in vacuum.
Further, the cerium-based metal organic framework (CeO)2NRs-MOF) was diluted with ultrapure water and dispersed to a suspension at a concentration of 1 mg/mL.
Secondly, the invention provides a preparation method of a cerium-based metal organic framework for Cr (VI) detection.
The preparation method comprises the following steps: (1) cerium dioxide nanorod (CeO)2NRs) preparation; (2) cerium-based metal organic framework (CeO)2NRs-MOF); (3) diluting and dispersing with ultrapure water: obtaining cerium-based metal organic framework (CeO) with the concentration of 1mg/mL2NRs-MOF).
Further, the cerium oxide nanorods (CeO) of step (1)2NRs) is prepared by the following steps: dissolving 1 part of cerous nitrate hexahydrate and 10-12 parts of sodium hydroxide in ultrapure water by mass part, stirring and mixing for 20-40 minutes, reacting for 20-30 hours at 95-105 ℃, cooling to room temperature, then sequentially centrifugally washing the product for 2-4 times by using ultrapure water and ethanol, and drying for 12-24 hours in vacuum at 50-70 ℃ to obtain CeO2And (4) nanorods.
Further, the cerium-based metal organic framework (CeO) of the step (2)2NRs-MOF), in particular: 1 part of CeO by mass2Mixing the nano-rod with 70-80 parts of DMF (N, N-dimethylformamide) solution containing terephthalic acid, reacting for 10-15 hours at 65-75 ℃, cooling to room temperature, sequentially centrifugally washing the product with DMF and ethanol for 2-4 times, and vacuum drying for 12-24 hours at 50-70 ℃ to obtain the cerium-based metal organic framework.
Finally, the invention provides the use of a cerium-based metal organic framework.
The cerium-based metal organic framework is used for detecting Cr (VI).
The detection of Cr (VI) is specifically as follows: based on volume fraction, cerium-based metal organic framework (CeO)21 part of NRs-MOF) suspension, 0.1 part of TMB (3,3',5,5' -tetramethylbenzidine) solution, 0.5 part of Cr (VI) solution with different concentrations in the range of 0-5 mu M and 0.5 part of HEPES (4-hydroxyethyl piperazine ethanesulfonic acid) buffer solution are mixed, ultrapure water is added for dilution to the total volume of the solution of 5 parts, mixing reaction is carried out, an ultraviolet-visible spectrophotometer is immediately adopted for measuring the absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800nm, and the Ling of Cr (VI) is realized according to the linear relationship between the TMB ultraviolet absorption spectrum intensity and the Cr (VI) concentrationAnd (4) carrying out sensitive detection.
Further, the concentration of the cerium-based metal organic framework suspension is 1 mg/mL; the concentration of the TMB solution is 20 mM.
Further, the HEPES buffer solution had a pH of 4 and a concentration of 100 mM.
Has the advantages that:
(1) the cerium-based metal organic framework synthesized by the sacrificial template method has the specific ratio of CeO2The nano material has stronger oxidase activity.
(2) The cerium-based metal organic framework synthesized by the invention can oxidize TMB to show blue, selectively adsorb high-toxicity Cr (VI) and reduce the Cr (III) to Cr (III) without H2O2In the presence of Cr (VI) instead of H2O2And TMB constitute a new redox cycle system.
(3) The invention combines the oxidase activity of the cerium-based metal organic framework with the new Cr (VI) -TMB system, constructs a novel colorimetric method for detecting Cr (VI), realizes the detection of Cr (VI) in the environmental water body, and has the advantages of high sensitivity, good selectivity, simplicity, rapidness and good application prospect.
Drawings
FIG. 1: TEM images of cerium-based metal organic frameworks. Wherein A is CeO2TEM image of NRs, B is CeO2TEM image of NRs-MOF;
FIG. 2: CeO (CeO)2NRs and CeO2UV-VISIBLE absorption spectrum of NRs-MOF in response to Cr (VI).
FIG. 3: based on CeO2Schematic diagram of the detection of Cr (VI) by the oxidase activity of NRs-MOF.
FIG. 4: and (3) detecting the UV-Vis spectrogram of Cr (VI) by a colorimetric method.
FIG. 5A: a colorimetric ultraviolet-visible absorption spectrum diagram responding to different concentrations of Cr (VI);
FIG. 5B: calibration curve between concentration of cr (vi) and TMB characteristic absorption peak intensity.
FIG. 6: selectivity graph of colorimetric method for Cr (VI) detection.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1: preparation of cerium-based metal organic frameworks
Dissolving 0.434g of cerous nitrate hexahydrate and 4.8g of sodium hydroxide in 20mL of ultrapure water, stirring and mixing for 30 minutes, placing the mixed solution in a high-pressure reaction kettle to react for 24 hours at 100 ℃, cooling to room temperature, sequentially using ultrapure water and ethanol to centrifugally wash the product for three times, placing the product in a vacuum drying oven for standing overnight at 60 ℃ to prepare CeO2A nanorod; 20mg of CeO2Mixing the nano-rod with 30mL of DMF solution containing 1.4952g of terephthalic acid, placing the mixture in a high-pressure reaction kettle for reaction at 70 ℃ for 12 hours, cooling the mixture to room temperature, sequentially using DMF and ethanol to centrifugally wash the product for three times, and placing the product in a vacuum drying oven at 60 ℃ for overnight to obtain a cerium-based metal organic framework (CeO)2NRs-MOF)。
Example 2: preparation of cerium-based metal organic frameworks
Dissolving 0.434g of cerous nitrate hexahydrate and 4.34g of sodium hydroxide in 20mL of ultrapure water, stirring and mixing for 20 minutes, placing the mixed solution in a high-pressure reaction kettle to react for 20 hours at 95 ℃, cooling to room temperature, sequentially using the ultrapure water and ethanol to centrifugally wash the product twice, and placing the product in a vacuum drying oven at 50 ℃ for 12 hours to prepare CeO2A nanorod; 20mg of CeO2Mixing the nano-rod with 30mL of DMF solution containing 1.4g of terephthalic acid, placing the mixture in a high-pressure reaction kettle for reaction at 65 ℃ for 10 hours, cooling the mixture to room temperature, sequentially centrifugally washing the product twice with DMF and ethanol, and placing the washed product in a vacuum drying oven at 60 ℃ for 12 hours to obtain a cerium-based metal organic framework (CeO)2NRs-MOF)。
Example 3: preparation of cerium-based metal organic frameworks
Dissolving 0.434g of cerous nitrate hexahydrate and 5.208g of sodium hydroxide in 20mL of ultrapure water, stirring and mixing for 40 minutes, placing the mixed solution in a high-pressure reaction kettle to react for 30 hours at 105 ℃, cooling to room temperature, and then centrifugally washing the product by sequentially using ultrapure water and ethanolWashing for four times, and then placing in a vacuum drying oven at 70 ℃ for 24 hours to obtain CeO2A nanorod; 20mg of CeO2Mixing the nano-rod with 30mL of DMF solution containing 1.6g of terephthalic acid, placing the mixture in a high-pressure reaction kettle for reaction at 75 ℃ for 15 hours, cooling the mixture to room temperature, sequentially centrifugally washing the product with DMF and ethanol for four times, and placing the product in a vacuum drying oven at 70 ℃ for 24 hours to obtain a cerium-based metal organic framework (CeO)2NRs-MOF)。
Example 4: characterization of cerium-based Metal organic frameworks
CeO obtained in example 1 was subjected to a Transmission Electron Microscope (TEM)2The morphology of the NRs-MOF was characterized and the results are shown in FIG. 1. Wherein A is CeO2TEM image of NRs, B is CeO2TEM image of NRs-MOF. From CeO2NRs and CeO2TEM image of NRs-MOF revealed, CeO2NRs and CeO2NRs-MOF are all rod-shaped structures, CeO2NRs having a width of about 5-10nm and a length of about 120nm, CeO2NRs-MOF in CeO2The NRs are surrounded by a thin layer of about 2-5nm in thickness.
By X-ray photoelectron spectroscopy (XPS) on CeO2And characterizing the element and valence composition of the NRs-MOF. CeO (CeO)2NRs and CeO2XPS spectrum of O1 s of NRs-MOF showed that CeO2NRs respectively show characteristic peaks of Ce (III) -O and Ce (IV) -O at 528.7eV and 530.4eV, and CeO2The characteristic peaks of NRs-MOF at 528.9eV and 530.7eV correspond to Ce (III) -O and Ce (IV) -O, respectively, indicating that CeO2NRs and CeO2NRs-MOFs both have mixed valence states of trivalent and tetravalent cerium, such that both possess oxidase activity; the peak-splitting integral calculation of XPS was further carried out, and the ratio of Ce (III) -O/Ce (IV) -O was 0.3874 to CeO20.2641 high for NRs indicating CeO2CeO content ratio of trivalent cerium in NRs-MOF2NRs is large, indicating that CeO2NRs-MOF having a ratio of CeO2The stronger oxidase activity of NRs, which is consistent with the increase of the activity of cerium oxide nanoenzymes reported in the literature with the increase of the content of trivalent cerium (Heckert, E.G.; Karakoti, A.S.; Seal, S.; Self, W.T. the roll of cerium redox state in the SOD nominal activity of nanoceria. biomaterials,2008,29(18),2705-The CeO with strong oxidase activity is prepared2NRs-MOF。
Ultraviolet-visible absorption (UV-Vis) spectrometry method for CeO2NRs and CeO2The oxidase activity of NRs-MOF was characterized, and FIG. 2 shows CeO2NRs and CeO2UV-Vis spectra of NRs-MOF response to Cr (VI). 100 mu L of 1mg/mL cerium-based metal organic framework, 10 mu L of 20mM TMB solution, 50 mu L of 10 mu M Cr (VI) solution and 50 mu L of 100mM HEPES buffer solution with pH 4 are mixed, ultrapure water is added until the total volume of the solution is 500 mu L, and after uniform mixing, an UV-2450 type ultraviolet-visible spectrophotometer is immediately adopted to measure the absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800 nm. CeO (CeO)2NRs cannot oxidize TMB in a short time, so the absorption peaks at 370nm and 650nm are very weak, while CeO2NRs-MOF has stronger oxidase activity and can rapidly oxidize TMB for color development, so that strong absorption peaks of oxidized TMB appear at 370nm and 650 nm.
Example 5: based on CeO2Principle and feasibility analysis for detecting Cr (VI) by oxidase activity of NRs-MOF
CeO prepared based on sacrificial template method2The steps for detecting Cr (VI) by NRs-MOF construction colorimetry are simple, and only CeO needs to be measured2And the ultraviolet spectral characteristics of the mixed solution of NRs-MOF, TMB and Cr (VI) are changed, so that the detection of the target object can be realized. With CeO2Comparison of the Nano-materials, CeO2NRs-MOF has stronger oxidase activity and selectivity and can be used in the absence of H2O2In the presence of the catalyst, TMB is directly oxidized to develop color and selectively adsorb Cr (VI) and reduce the Cr (VI) to Cr (III), wherein the Cr (VI) can replace H used conventionally2O2And forms a new oxidation-reduction cycle system with TMB to realize the rapid colorimetric method for detecting Cr (VI). The detection principle is shown in fig. 3.
The feasibility of the colorimetric method constructed by the invention is verified by using a UV-Vis spectrum method, and FIG. 4 is a UV-Vis spectrum diagram for detecting Cr (VI) by using the colorimetric method constructed by the invention under different experimental conditions. As can be seen from FIG. 4, in an aqueous solution containing 10mM HEPES pH 4, CeO2NRs-MOF (labeled CeO in the figure)2None of MOF), TMB and Cr (VI) has a characteristic absorption peak in the wavelength range of 330nm to 800nm, andthe three components are mixed in pairs, and no obvious characteristic absorption peak appears, only in CeO2The existence of NRs-MOF, TMB and Cr (VI) can cause obvious characteristic absorption peaks of oxidized TMB at 370nm and 650 nm. The above results show that CeO prepared by the method of the present invention2NRs-MOF has good oxidase activity, and is combined with a Cr (VI) -TMB redox new system to successfully construct a new colorimetric method and can be used for detecting Cr (VI).
Example 6: based on CeO2Analysis of detection performance of colorimetric method constructed by NRs-MOF on Cr (VI)
Diluting and dispersing the cerium-based metal organic framework obtained in the embodiment 1 into 100 muL suspension with the concentration of 1mg/mL, 10 muL solution of 20mM TMB, 50 muL solution of Cr (VI) with different concentrations in the range of 0-5 muM and 50 muL HEPES buffer solution with the pH value of 100mM 4 by using ultrapure water, adding the ultrapure water until the total volume of the solution is 500 muL, and immediately measuring the absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800nm by using a UV-2450 type UV-visible spectrophotometer after uniform mixing, wherein the UV-visible absorption spectrogram responding to Cr (VI) with different concentrations by using the colorimetric method constructed by the invention is shown in a figure 5A; the calibration curve between the concentration of Cr (VI) and the intensity of the TMB characteristic absorption peak is shown in FIG. 5B.
As can be seen from FIG. 5A, as the Cr (VI) concentration increases (0,0.03,0.05,0.1,0.2,0.4,0.6,0.8,1,2,3,4 and 5. mu.M), the blue color of the solution becomes gradually darker and the absorption peak intensity at 650nm becomes gradually stronger; as can be seen from fig. 5B, the difference between the absorbance at 650nm and the absorbance at the baseline at 750nm (Δ a ═ a)650nm-A750nm) Has good linear relation with Cr (VI) concentration in the range of 30nM-5 μ M, and the detection limit is 20 nM. Detection of Cr (VI) in comparison with a colorimetric method based on coordination of gold nanoparticles (linear range 0.5-2.5. mu.M, detection limit 0.07. mu.M) (Du, J.; Ge, H.; Gu, Q.; Du, H.; Fan, J.; Peng, X.Goldnanoparticles-based no-probe for the colorimetric detection of Cr3+and Cr2O7 2-by the coordination strategy, nanoscale,2017,9(48),19139-4+MOF specific adsorption and detection of Cr (VI) (detection range 0.5-96 μ M, limit of detection 77nM) (Rapti, S.; Sarma, D.; Diamantis, S.A.; Skliri, E.; Armatas, G.S.; Tsipis, A.C.; Hassa)n,Y.S.；Alkordi,M.；Malliakas,C.D.；Kanatzidis,M.G.；Lazarides T.；Plakatouras,J.C.；Lazarides,T.All in oneporous material:exceptional sorption and selective sensing of hexavalentchromium by using a Zr4+Journal of Materials Chemistry a,2017,5(28), 14707-; zhou, h.; gao, r.; zhang, y.; zhang, h.; zhang, y.; wang, g.; wong, p.k.; ZHao, H.Selective determination of Cr (VI) by fluorinated cross-linked chitosan. ACS sensors,2018,3(4),792-798) are effective. Therefore, the cerium-based metal organic framework prepared by the method has good sensitivity and reliability when used for detecting Cr (VI).
Example 7: based on CeO2Selectivity of colorimetric method constructed by NRs-MOF on Cr (VI) detection
Examine the content of the substances based on CeO2The selectivity of colorimetric method constructed by NRs-MOF for Cr (VI) detection is shown in FIG. 6. As can be seen from FIG. 6, the 17 types of water may have cations and anions present in concentrations that are ten times the concentration of Cr (VI), e.g., 1 μ M for Cr (VI) and 10 μ M for other ions, with little response. This is due to CeO2Size selection effect of MOFs of NRs-MOF outer layer and absence of H in color development system2O2Avoids the dual function of ion interference (such as iron ion and copper ion) with peroxidase activity. In conclusion, the method has good selectivity for detecting Cr (VI).
Similarly, the cerium-based metal organic framework prepared in example 2 and the cerium-based metal organic framework prepared in example 3 were subjected to the same procedures as in examples 4 to 7, and the results of the tests and experiments were substantially the same as those of examples 4 to 7, which were carried out on the cerium-based metal organic framework prepared in example 1.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the above-described embodiments. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent alterations and modifications are intended to be included within the scope of the invention, without departing from the spirit and scope of the invention.
Claims (10)
1. A cerium-based metal organic framework for cr (vi) detection, characterized by: by using cerium dioxide nano rod CeO with simulated enzyme activity2NRs is used as a template, cerium ions are provided as ion centers, terephthalic acid is added, and CeO is formed through nucleation and growth2NRs-MOF metal organic frameworks.
2. The cerium-based metal-organic framework for cr (vi) detection according to claim 1, wherein: the cerium dioxide nanorod CeO2NRs are prepared by mixing and reacting cerous nitrate hexahydrate and sodium hydroxide, centrifuging, washing and drying in vacuum.
3. The cerium-based metal-organic framework for cr (vi) detection according to claim 1, wherein: the CeO2NRs-MOF metal organic framework is diluted by ultrapure water and dispersed into suspension with the concentration of 1 mg/mL.
4. A preparation method of a cerium-based metal organic framework for Cr (VI) detection is characterized in that: the method comprises the following steps: (1) cerium dioxide nanorod CeO2Preparing NRs; (2) CeO (CeO)2Nucleation of NRs-MOF metal-organic frameworks; (3) diluting and dispersing with ultrapure water: CeO with the concentration of 1mg/mL is obtained2A suspension of NRs-MOF metal organic frameworks.
5. The method of claim 4, wherein the cerium oxide nanorods CeO and/or CeO in step (1) are used for detecting Cr (VI)2NRs are prepared by the following steps: dissolving 1 part of cerous nitrate hexahydrate and 10-12 parts of sodium hydroxide in ultrapure water by mass part, stirring and mixing for 20-40 minutes, and mixing for 95-1Reacting at 05 ℃ for 20-30 hours, cooling to room temperature, then centrifugally washing the product with ultrapure water and ethanol for 2-4 times in sequence, and drying in vacuum at 50-70 ℃ for 12-24 hours to obtain cerium dioxide nanorod CeO2NRs。
6. The method of claim 4, wherein the CeO in step (2) is used as a cerium-based metal organic framework for Cr (VI) detection2Nucleation of the metal-organic framework of the NRs-MOF is specifically as follows: 1 part of cerium dioxide nano rod CeO by mass2NRs and DMF solution containing 70-80 parts of terephthalic acid are mixed, reacted for 10-15 hours at 65-75 ℃, cooled to room temperature, and then the product is centrifugally washed for 2-4 times by DMF and ethanol in sequence, and dried for 12-24 hours in vacuum at 50-70 ℃ to obtain CeO2NRs-MOF metal organic frameworks.
7. Use of a cerium-based metal organic framework according to any one of claims 1 to 3, characterized in that: applied to the detection of Cr (VI).
8. The use of a cerium-based metal organic framework according to claim 7, wherein said detection of Cr (VI) is in particular: calculated by volume portion, CeO21 part of suspension of NRs-MOF metal organic framework, 0.1 part of TMB solution, 0-5 mu M Cr (VI) solution with different concentrations and 0.5 part of HEPES buffer solution are mixed, ultrapure water is added for dilution to 5 parts of the total volume of the solution for mixing reaction, the absorption spectrum of the mixed reaction solution in the wavelength range of 330nm-800nm is immediately determined, and the sensitive detection of Cr (VI) is realized according to the linear relationship between the TMB ultraviolet absorption spectrum intensity and the Cr (VI) concentration.
9. Use of a cerium-based metal organic framework according to claim 8, characterized in that: the cerium-based metal organic framework suspension is 1 mg/mL; the concentration of the TMB solution is 20 mM.
10. The use of a cerium-based metal organic framework according to claim 8, wherein said HEPES buffer solution has a pH of 4 and a concentration of 100 mM.
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