CN113559880B - Pd@NiCo 2 O 4 Double-function nano imitation enzyme and preparation method and application thereof - Google Patents
Pd@NiCo 2 O 4 Double-function nano imitation enzyme and preparation method and application thereof Download PDFInfo
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- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 90
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- 238000001514 detection method Methods 0.000 claims abstract description 22
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- 239000002243 precursor Substances 0.000 claims abstract description 15
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/391—Physical properties of the active metal ingredient
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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Abstract
The invention relates to the technical field of heavy metal mercury detection, in particular to Pd@NiCo 2 O 4 A double-function nanometer enzyme imitation and its preparation method and application are provided. The nano-mimic enzyme comprises: niCo 2 O 4 A substrate and Pd nano particles, wherein the Pd nano particles are of tetrahedron/triangular pyramid structure and are loaded on the NiCo 2 O 4 On the substrate. The method comprises the following steps: (1) Providing a composition containing Co 2+ Ion, ni 2+ Ions, pd 2+ Adding ammonia water and glycol into the mixed solution of ions and polyvinylpyrrolidone, and uniformly mixing to obtain a precursor mixed solution; (2) And (3) treating the precursor mixed solution by microwaves, and separating out a solid product after the reaction is finished to obtain the precursor. The invention synthesizes Pd@NiCo under the template guidance of PVP 2 O 4 The double-function simulated oxidase/peroxidase performance is provided, and the double-function simulated oxidase/peroxidase can be used for efficiently performing visual colorimetric detection on trace heavy metal mercury in samples such as environmental water, biology, medicines and the like.
Description
Technical Field
The invention relates to the technical field of heavy metal mercury detection, in particular to Pd@NiCo 2 O 4 A double-function nanometer enzyme imitation and its preparation method and application are provided.
Background
The information disclosed in the background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
The nanometer mimic enzyme/enzyme serving as a high-efficiency bionic catalyst has higher substrate specificity, selectivity and catalytic efficiency, and high stability, and can catalyze certain colorimetric substrates to generate special color reaction under mild conditions, so that colorimetric signals are amplified, and the nanometer mimic enzyme/enzyme has been widely applied to fields of bionic catalysis, biosensing, environmental analysis and detection and the like.
Mercury is one of the most toxic and polluting heavy metal pollutants, cannot be degraded or biologically transformed in natural environment, is easily aggregated in organisms, and has strong sulfur-philic performance (such as-SH groups), so that biological proteins or biological enzymes are denatured and deactivated, and the health of human beings is seriously threatened. For this reason, the world health organization limits the content of heavy metal mercury in drinking water to not more than 3.0X10 -8 mol/L。
However, the inventor discovers that the conventional metal-based nano-mimic enzyme has the problems of relatively simple components, single morphology, single function catalytic performance and the like, so the inventor considers that the multi-component and multifunctional nano-mimic enzyme with strong synergistic effect of the components and the morphology is developed, discusses the application of the multi-component and multifunctional nano-mimic enzyme in high-efficiency, convenient and sensitive detection of heavy metal mercury ions, and has important significance in effectively eliminating pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a Pd@NiCo 2 O 4 The invention discloses a difunctional nano-imitation enzyme and a preparation method and application thereof, and synthesizes a two-dimensional cobalt nickel oxide stabilized palladium nano tetrahedral composite material under the template guidance of polyvinylpyrrolidone (PVP): pd@NiCo 2 O 4 The method can be used for efficiently carrying out visual colorimetric detection on trace heavy metal mercury in samples such as environmental water, biology, medicines and the like.
Specifically, in order to achieve the above object, the technical scheme of the present invention is as follows:
in a first aspect of the invention, a maleOpen a Pd@NiCo 2 O 4 A nano-mimic enzyme comprising: niCo 2 O 4 A substrate, pd nanoparticles, wherein: the Pd nano-particles are of tetrahedron/triangular pyramid structure and are loaded on the NiCo 2 O 4 On the substrate.
Further, the Pd nano-particles and NiCo 2 O 4 The substrates are connected by metal bonding between Pd and Ni and/or Co atoms.
Further, the particle size of the Pd tetrahedral nano particles is between 10 and 15nm, and the Pd tetrahedral nano particles are uniformly dispersed in the NiCo through the common free electron effect of metal bonds among Pd, ni or Co 2 O 4 On the surface of the substrate, thereby making Pd@NiCo 2 O 4 Oxidation mimic enzyme and NiCo with nano Pd 2 O 4 The peroxidation mimic enzyme performance of the (2) has good synergistic enhancement effect; in addition, the Pd tetrahedral nano-particles have different surfaces, lines and point catalytic active sites, and different surface energies can endow the tetrahedral Pd nano-particles with special catalytic activity.
Further, the NiCo 2 O 4 The substrate is of a two-dimensional sheet structure, so that an ultra-large specific surface area is provided for the loading of Pd nano-particles.
In a second aspect of the invention, a Pd@NiCo is disclosed 2 O 4 The preparation method of the nanometer enzyme imitation comprises the following steps:
(1) Providing a composition containing Co 2+ Ion, ni 2+ Ions, pd 2+ And adding glycol into the alkaline mixed solution of ions and polyvinylpyrrolidone, and uniformly mixing to obtain the precursor mixed solution.
(2) And (3) treating the precursor mixed solution by microwaves, separating out a solid product after the reaction is finished, and removing a template formed by polyvinylpyrrolidone to obtain the modified polyvinyl pyrrolidone.
Further, in the step (1), co 2+ Ion source, ni 2+ Ion source, pd 2+ And dispersing the ion source in the neutral polyvinylpyrrolidone solution, stirring uniformly, adding ammonia water and ethylene glycol, and continuously stirring to obtain the precursor mixed solution.
Further, the Co 2+ The ion source includes: co (NO) 3 ) 2 、CoSO 4 、CoCl 2 、Co(CH 3 COO) 2 At least one of the following.
Further, the Ni 2+ The ion source includes: ni (NO) 3 ) 2 、NiSO 4 、NiCl 2 、Ni(CH 3 COO) 2 At least one of the following.
Further, the Pd 2+ The ion source includes: na (Na) 2 PdCl 4 、K 2 PdCl 4 、Pd(CH 3 COO) 2 、PdCl 2 At least one of the following.
Further, in step (1), the Co 2+ Ion, ni 2+ Ions, pd 2+ The proportion of the ions and polyvinylpyrrolidone is 0.2-0.5 mmol:0.1 to 0.4mmol:0.05 to 0.1mmol: 160-300 mg.
Further, in the step (1), the alkaline mixed solution is formed by adding ammonia water, and optionally, the volume ratio of the ammonia water to the ethylene glycol is 100-500 μl: 10-50 mL, wherein the concentration of the ammonia water is 25-28%. In the invention, the ammonia water can provide a weak alkaline environment to enable Ni/Co ions to form hydroxide and simultaneously can be combined with Pd 2+ Coordination, forming tetrahedral complexes.
Further, the Co is dispersed by ultrasonic 2+ Ion source, ni 2+ Ion source, pd 2+ The ion source is dispersed in the neutral polyvinylpyrrolidone solution to promote the dispersion of each metal ion in the polyvinylpyrrolidone solution.
Further, in the step (2), the power of the microwave treatment is 450-700W, and the treatment time is 10-25 min. Microwaves are a special heating mode from inside to outside, and through microwave treatment, the microwave treatment has the advantages of rapid heating, homogeneous reaction, high selectivity, promotion of reaction, improvement of crystallinity of synthesized nanocrystals and the like.
Further, in the step (2), the solid product is centrifugally separated, and then centrifugally washed by ethanol and water, and the solid product is dried in vacuum after the completion of the centrifugal washing, thus obtaining the target productTarget product Pd@NiCo 2 O 4 Nanometer enzyme imitation.
In a third aspect of the present invention, the Pd@NiCo is disclosed 2 O 4 The nanometer enzyme imitation is applied to the fields of environmental water, biology, medicine and the like.
Further, the application is to utilize the Pd@NiCo 2 O 4 Heavy metal Hg by nanometer enzyme imitation 2+ The test method of (2) comprises the following steps:
s1, pd@NiCo 2 O 4 Adding colorimetric substrate 3,3', 5' -tetramethyl benzidine (TMB), disodium hydrogen phosphate-citric acid buffer solution and H into standard solution 2 O 2 And (5) obtaining the sample liquid to be detected.
S2, observing the color change of the liquid to be detected.
Further, in the step S1, the standard solution is Pd@NiCo with the concentration of 0.1mg/mL 2 O 4 A solution.
Further, in step S2, the color change is a visible color change from light blue to dark blue, that is, the sample liquid to be measured contains Hg 2+ 。
The Pd@NiCo of the invention 2 O 4 Imitation enzyme detection of heavy metal Hg by TMB system 2+ The principle of (2) is as follows: double-function nano enzyme Pd@NiCo 2 O 4 Catalytic oxidation of 3,3', 5' -Tetramethylbenzidine (TMB) in air to form the blue oxide oxTMB having an oxidation potential of H 2 O 2 Further enhancement in the presence and characteristic UV-visible absorption peaks at 652 nm. When there is trace heavy metal Hg 2+ In the presence of the catalyst, the oxidation potential is larger than that of Pd, pd@NiCo 2 O 4 Pd in (3) 0 Hg can be used to make Hg 2+ Reducing to elemental mercury, further forming Pd-Hg alloy on the nano surface of palladium, enhancing the catalytic activity of nano enzyme, pd@NiCo 2 O 4 The color of the TMB system is further darkened and the UV-visible absorption peak at 652nm is intensified.
Compared with the prior art, the invention has the following beneficial effects:
(1) Is prepared from neutral polyvinyl pyrrolidone (PVP)Under the guidance of a template, a two-dimensional cobalt nickel oxide composite tetrahedron nano palladium imitation enzyme (Pd@NiCo) is synthesized through microwave-assisted optimization 2 O 4 ) Wherein: the NiCo 2 O 4 The substrate is loaded on the PVP template through the action of empty d orbits on Ni and/or Co atoms and PVP electron-rich coordination bonds, the PVP template is soluble, can be conveniently removed in the process of water centrifugal washing after synthesis, and the PVP template can lead NiCo to be removed 2 O 4 And a two-dimensional structure is formed, so that irregular nano particles are avoided. Tetrahedral Pd particles are uniformly dispersed in the NiCo through the common free electron effect of metal bonds among Pd, ni or Co 2 O 4 On the surface of the substrate, thereby making Pd@NiCo 2 O 4 Oxidation mimic enzyme and NiCo with nano Pd 2 O 4 The peroxidation mimic enzyme performance of the (2) has good synergistic enhancement effect; in addition, the Pd tetrahedral nano-particles have different surfaces, lines and point catalytic active sites, and different surface energies can endow the tetrahedral Pd nano-particles with special catalytic activity.
(2) Pd@NiCo synthesized by the method 2 O 4 The nanometer mimic enzyme has good nanometer mimic oxidase activity or mimic peroxidase activity, namely difunctional nanometer enzyme; particularly, 3', 5' -tetramethyl benzidine (TMB) can be rapidly catalyzed and oxidized to generate blue oxide oxTMB under the conditions of room temperature and air in the presence of ultra-trace mercury ions, has strong visual sensitization effect, and Pd@NiCo 2 O 4 The activity of the nanometer mimic enzyme is shown in H 2 O 2 Further strengthening in the presence and generating characteristic ultraviolet-visible absorption peak at 652nm, so as to be convenient for efficiently treating ultra-trace Hg in environmental water, commercial fruit juice beverage and the like 2+ The visual detection of the method is convenient and quick, the sensitivity is high, and the detection result is accurate.
(3) The Pd@NiCo of the invention 2 O 4 Nanometer enzyme-like catalysis TMB and H 2 O 2 Miq constants (Km) of 0.047mM and 0.25mM, respectively, and maximum onset rates (Vmax) of 2.13×10, respectively -8 M·s -1 And 3.08X10 -8 M·s -1 . Can be used for environmental water, biology and medicineThe detection limit of the visible colorimetric detection of trace heavy metal mercury in the sample can reach 9.5 multiplied by 10 -10 M, hg in sample 2+ The recovery rate is 97.4-102.6%, the relative error (RSD) is less than 3.7%, and the catalytic activity of the mimic enzyme and the sensitivity of colorimetric detection of heavy metal mercury ions are effectively ensured.
(4) Through testing, common coexisting ions (such as Ag + 、Ba 2+ 、Bi 3+ 、Ca 2+ 、Co 2+ 、Cr 3+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、K + 、Mn 2+ 、Ni 2+ 、Pb 2+ 、Zn 2+ Etc.) contrast color detection Hg 2+ No obvious interference, the Pd@NiCo synthesized by the invention 2 O 4 The nanometer mimic enzyme has good anti-interference performance and shows that the nanometer mimic enzyme has good anti-interference performance on Hg 2+ Excellent specificity and selectivity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows Pd@NiCo prepared in accordance with a first embodiment of the invention 2 O 4 TEM of nano-mimic enzyme.
FIG. 2 shows Pd@NiCo prepared in accordance with a first embodiment of the invention 2 O 4 Element analysis EDS of the nanometer imitation enzyme; wherein: the inset is HR-TEM.
FIG. 3 is a graph of Pd@NiCo prepared in accordance with a first embodiment of the invention 2 O 4 XPS profile (panel a) and XRD profile (panel b) of the nano-mimic enzyme.
FIG. 4 shows Pd@NiCo prepared in accordance with the first embodiment of the invention 2 O 4 Nanometer enzyme imitation in N 2 、O 2 、H 2 O 2 Or O 2 /H 2 O 2 The enzyme activity contrast and color change profile (inset) were simulated in the presence of the same.
FIG. 5 shows the pH of the system, the molar ratio of the material components, the reaction temperature, TMB concentration, H 2 O 2 Concentration, reaction time vs. Pd@NiCo prepared in the first example of the invention 2 O 4 Graph of the effect of nano enzyme activity.
FIG. 6 shows Pd@NiCo prepared in accordance with the first embodiment of the invention 2 O 4 Kinetic curve of nano enzyme imitation.
FIG. 7 shows Pd@NiCo prepared in accordance with the first embodiment of the invention 2 O 4 Nanometer imitation enzyme along with H 2 O 2 A double reciprocal plot of TMB concentration change; wherein: graph c is a double reciprocal plot of TMB concentration change, graph d is H 2 O 2 Double reciprocal plot of concentration change.
FIG. 8 shows different interfering ions (Ag + 、Ba 2+ 、Bi 3+ 、Ca 2+ 、Co 2+ 、Cr 3+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、K + 、Mn 2+ 、Ni 2 + 、Pb 2+ 、Zn 2+ ) For Pd@NiCo prepared in the first example 2 O 4 The effect of spectral properties of the nanoshaptens (panel a) and the colorimetric properties (panel b).
FIG. 9 is a graph of interfering ions and Hg 2+ In the coexistence, pd@NiCo prepared in the first embodiment of the invention 2 O 4 And (5) an influence diagram of the spectral performance of the nanometer enzyme imitation.
FIG. 10 is a colorimetric sensing of heavy metal Hg 2+ Wherein: the curves from top to bottom represent Hg in this order 2+ The concentration is as follows: 0. 0.4, 0.8, 1.6, 2.4, 4.0, 6.0, 10.0, 15.0, 20.0, 38.0, 64.0, 80.0, 100.0, 120.0X10 -8 M, the illustration is a color change picture.
FIG. 11 shows Pd@NiCo prepared in accordance with the first embodiment of the invention 2 O 4 Light absorption intensity of nano enzyme-like (A) 653 ) And the concentration of mercury ions (c Hg 2+ ) Linear relationship between the two.
Detailed Description
In the following description, specific details of the invention are set forth in order to provide a thorough understanding of the invention. The terminology used in the description of the invention herein is for the purpose of describing the advantages and features of the invention only and is not intended to be limiting of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The medicines or reagents used in the present invention are used according to the product instructions or by the conventional methods of use in the art unless specifically stated. The technical scheme of the invention is further described according to the attached drawings and the specific embodiments.
First embodiment
Pd@NiCo 2 O 4 The preparation method of the double-function nanometer imitation enzyme comprises the following steps:
(1) Accurately weighing 116.4mg (0.4 mmol) Co (NO) 3 ) 2 ·9H 2 O、58.2mg(0.2mmol)Ni(NO 3 ) 2 ·6H 2 O and 9.8mg (0.067 mmol) Na 2 PdCl 4 Ultrasonic dispersion in 5mL of neutral polyvinylpyrrolidone (PVP, M) 40mg/mL W 30000 A) in solution. After continuously stirring for 10min, 300 mu L of ammonia water with the mass concentration of 25% and 30mL of ethylene glycol are added, and stirring is continued for 1h, so that a precursor mixed solution is obtained.
(2) Transferring the precursor mixed solution obtained in the step (1) into a microwave synthesizer, reacting for 20min by microwaves (600W, 140 ℃), cooling to room temperature, centrifuging with ethanol and water (the rotation speed is 6000 rpm) respectively, washing for 3 times, removing template PVP, and vacuum drying the solid product obtained by centrifuging at 60 ℃ to obtain Pd@NiCo 2 O 4 Nanometer enzyme imitation.
Second embodiment
Pd@NiCo 2 O 4 The preparation method of the double-function nanometer imitation enzyme comprises the following steps:
(1) Accurately weigh 0.5mmol CoSO 4 ·7H 2 O、0.4mmol NiSO 4 ·7H 2 O and 0.1mmol Pd (CH) 3 COO) 2 Ultrasonic dispersion in 7.5mL neutral polyvinylpyrrolidone 40mg/mL (PVP, M W 30000 A) in solution. After stirring continuously for 15min, 500 mu L of ammonia water with the mass concentration of 25% and 50mL of glycol are added for stirring continuouslyAnd (3) 1h, obtaining a precursor mixed solution.
(2) Transferring the precursor mixed solution obtained in the step (1) into a microwave synthesizer, reacting for 10min by microwaves (700W and 140 ℃), cooling to room temperature, centrifuging with ethanol and water (the rotation speed is 6000 rpm) respectively, washing for 3 times, removing template PVP, and vacuum drying the solid product obtained by centrifuging at 60 ℃ to obtain Pd@NiCo 2 O 4 Nanometer enzyme imitation.
Third embodiment
Pd@NiCo 2 O 4 The preparation method of the double-function nanometer imitation enzyme comprises the following steps:
(1) Accurately weigh 0.2mmol CoCl 2 ·6H 2 O、0.1mmol NiCl 2 ·6H 2 O and 0.05mmol PdCl 2 ·2H 2 O ultrasonic dispersion in 4mL neutral polyvinylpyrrolidone (PVP, M) 40mg/mL W 30000 A) in solution. After continuously stirring for 10min, 100 mu L of ammonia water with the mass concentration of 28% and 10mL of ethylene glycol are added, and stirring is continued for 1h, so as to obtain a precursor mixed solution.
(2) Transferring the precursor mixed solution obtained in the step (1) into a microwave synthesizer, reacting for 25min by microwaves (450W and 140 ℃), cooling to room temperature, centrifuging with ethanol and water (the rotation speed is 6000 rpm) respectively, washing for 3 times, removing template PVP, and vacuum drying the solid product obtained by centrifuging at 60 ℃ to obtain Pd@NiCo 2 O 4 Nanometer enzyme imitation.
Performance characterization, testing:
1. Pd@NiCo prepared in the first embodiment by adopting transmission electron microscope 2 O 4 The results of microscopic observation and component detection by the nano enzyme imitation are shown in fig. 1 to 3. As can be seen from FIG. 1, the Pd nanoparticles prepared are tetrahedral in structure and are dispersed uniformly in two-dimensional NiCo 2 O 4 On the substrate, the grain diameter is 10-15 nm, wherein, the two-dimensional NiCo 2 O 4 The substrate can provide a super large specific surface area for the loading of Pd nano-particles, thereby providing a large number of catalytic reaction active sites, and the tetrahedral Pd nano-particles have special catalytic activity. Further, as can be seen from FIG. 2The apparent lattice spacing of three kinds of 0.225nm, 0.240nm and 0.250nm are respectively attributed to the (111) crystal face of Pd and NiCo 2 O 4 The (311) and (220×311) crystal planes. As can be seen from fig. 3a, the XPS spectrum contains all the elements Pd, co, ni, O; FIG. 3b shows two-dimensional NiCo 2 O 4 A characteristic crystal diffraction signal of the substrate (2θ= 31.6,36.5,44.3,54.8,59.0,64.7 and 71.6) and a characteristic crystal diffraction signal of nano Pd (2θ= 41.9,47.6and 67.9).
2. Pd@NiCo of the first embodiment 2 O 4 The detection capability test of the nano enzyme imitation on heavy metal ions comprises the following steps:
(1)0.1mg/mL Pd@NiCo 2 O 4 preparing a standard solution: weighing 0.01g of Pd@NiCo 2 O 4 Dispersing the sample into 100mL of purified water under ultrasonic condition to prepare Pd@NiCo with the concentration of 0.1mg/mL 2 O 4 The standard solution is preserved in the dark at room temperature for standby.
(2)Hg 2+ Preparing a standard solution: into a 100mL volumetric flask was added 0.0027g HgCl 2 After complete dissolution, the volume is fixed to 100mL by water to prepare the water with the concentration of 1.0X10 -4 mol/L, and storing at room temperature for standby.
(3) Preparing a sample to be tested: randomly weighing 1 part of each of 50.0mL urine sample, environmental water, commercial fruit juice beverage and medicament sample, filtering three times by a 4 mu m microporous filter membrane to obtain a sample to be detected, and storing the sample to be detected in a refrigerator (4 ℃) for later use.
(4)Pd@NiCo 2 O 4 Test of simulated oxidase catalytic activity: 400. Mu.L (0.1 mg/mL) of Pd@NiCo was measured 2 O 4 The NS standard solution and 100. Mu.L (1.5 mM) TMB were placed in a 3mL volumetric flask, thoroughly mixed, fixed to 3.0mL with disodium hydrogen phosphate-citric acid buffer solution (pH=4.0), aged at room temperature for 40min, measured for UV-visible absorption spectrum, measured for absorption spectrum in the range of 250 to 800nm, and the absorption intensity at 652nm was recorded (A 652 ) And the change in color of the solution was observed.
(5)Pd@NiCo 2 O 4 Test of simulated peroxidase catalytic activity: 400. Mu.L of the Pd@NiCo is measured 2 O 4 Standard solution, 100. Mu.L (1.5 mM) TMB and 100. Mu.L (1.5 mM) H 2 O 2 Placing into a 3mL volumetric flask, mixing thoroughly, fixing volume to 3.0mL with disodium hydrogen phosphate-citric acid buffer solution (pH=4.0), aging at room temperature for 40min, measuring ultraviolet-visible absorption spectrum, measuring absorption spectrum in 250-800 nm, recording absorption intensity at 652nm (A) 652 ) And the color change of the solution was observed.
The results are shown in fig. 4, and it can be seen that: at N 2 Pd@NiCo in atmosphere 2 O 4 TMB system is colorless and has weak absorption intensity at 652 nm; in air or H 2 O 2 Pd@NiCo in the presence of 2 O 4 The nanometer enzyme imitation can catalyze and oxidize TMB into light blue oxTEM at normal temperature, and obvious ultraviolet-visible characteristic absorption peak is generated at 652 nm; further adding a proper amount of H in the presence of oxygen 2 O 2 The absorption intensity and the color of the system at 652nm are obviously enhanced. Indicating Pd@NiCo 2 O 4 Has dual-function nanometer simulated oxidase activity or simulated peroxidase activity, and can be used for treating oxygen and H 2 O 2 Meanwhile, the synergistic effect is very strong in the presence.
(6) Optimization of enzyme activity experimental conditions: to obtain the optimal Pd@NiCo 2 O 4 The experiment discusses the pH of the system, the mole ratio of the material components, the reaction temperature, the TMB concentration and H 2 O 2 The effects of factors such as the concentration and reaction time, namely, the pH (2.5 to 7.0), pd/Co molar ratio (1:10 to 1:4), reaction temperature (20 to 50 ℃ C.), TMB content (0.01 to 0.10 mM) or H were investigated according to the methods of (4) and (5) above 2 O 2 (0.05-0.45 mM) for Pd@NiCo 2 O 4 Influence of nano enzyme-like catalytic activity.
The results are shown in fig. 5 to 7, and can be seen from fig. 5: under optimized conditions (pH=4.0, 0.06mM TMB, aging at 30℃for 40min or pH=4.0, 0.09mM TMB,0.30mM H) 2 O 2 Aging for 40min at 30 ℃), pd@NiCo 2 O 4 The nanometer mimic enzyme has good nanometer mimic oxidase activity or mimic peroxidase activity; from FIGS. 6andit can be seen in 7 that: the Pd@NiCo 2 O 4 Nanometer enzyme-like catalysis TMB and H 2 O 2 Miq constant (K) m ) Maximum initiation rate (V) max ) 2.13×10 respectively -8 M·s -1 And 3.08X10 -8 M·s -1 This means Pd@NiCo 2 O 4 The nanometer enzyme imitation has good enzyme imitation catalytic activity and catalytic rate, and can rapidly catalyze TMB and H 2 O 2 And (3) completely reacting the substrate to realize detection of the target object to be detected.
(7) FIGS. 8 and 9 investigate the common ambient metal ion pair Pd@NiCo 2 O 4 As can be seen from fig. 8 and 9, the activity selectivity of the nano enzyme imitation can be shown, under the existence of trace heavy metal mercury ions, the nano enzyme imitation can synergistically catalyze and oxidize colorimetric substrates 3,3', 5' -tetramethyl benzidine (TMB) to generate blue oxide oxTMB, and has a very strong visual sensitization effect; pd@NiCo 2 O 4 The activity of the nanometer mimic enzyme is in trace Hg 2+ Further strengthens the environment in the presence, is convenient for efficiently treating ultra-trace Hg in environmental water, commercial fruit juice beverage and the like 2+ Visual inspection of (c).
Meanwhile, common coexisting ions in the sample are detected: ag (silver) + 、Ba 2+ 、Bi 3+ 、Ca 2+ 、Co 2+ 、Cr 3+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、K + 、Mn 2+ 、Ni 2+ 、Pb 2+ 、Zn 2+ Detection of Hg with equal contrast color 2+ No obvious interference, pd@NiCo 2 O 4 -TMB System vs Hg 2+ Has specific selective colorimetric response and is accompanied by color change from colorless to blue, thereby leading Pd@NiCo 2 O 4 The nanometer imitation enzyme can detect the fine trace elements in the sample with the naked eyes rapidly and efficiently without the help of other observation instruments.
(8) The method for detecting the mercury ion content by enzyme catalysis and colorimetry comprises the following steps: 400. Mu.L of the Pd@NiCo was taken 2 O 4 Standard solution in a 3mL volumetric flask, 180 μl (1.5 mM) of TMB and 200 μl of disodium hydrogen phosphate-citric acid buffer solution with ph=4.0, 180 μl (1.0M) of H were added 2 O 2 And 100. Mu.L of Hg at different concentrations of 100. Mu.L 2+ And (3) uniformly mixing the standard solution or the sample to be tested, fixing the volume to 3.0mL by using a disodium hydrogen phosphate-citric acid buffer solution (pH=4.0), standing at room temperature for 40min, measuring the UV-vis absorption spectrum and the color change within the range of 300-800 nm, and comparing the UV-vis absorption spectrum and the color change with each other. According to absorbance at 653nm (A 653 ) With Hg 2+ Concentration (c) Hg 2 + ) Linear relation among the Hg and Hg in the sample to be measured is calculated 2+ Is a concentration of (3).
As a result, pd@NiCo was studied as shown in FIGS. 10 and 11 2 O 4 Absorption intensity of TMB System at 652nm (A 652 ) And c Hg 2+ The relation between the two shows that: pd@NiCo 2 O 4 Absorption intensity of TMB System at 652nm (A 652 ) Pair c Hg 2+ There is a special linear ratio relationship between partitions, namely: at 0.0 to 50.0X10 -9 M c Hg 2+ Within the range, the linear regression equation is A 652 ＝0.0061c Hg 2+ +0.3691(R 2 = 0.9883); at 50.0 to 400.0X10 -9 M c Hg 2+ Within the range, the linear regression equation is A 652 ＝0.0012c Hg 2+ +0.6348(R 2 = 0.9964), the lowest detection limit is as low as 9.5×10 -10 M. According to absorbance at 653nm (A 653 ) With Hg 2+ Concentration (c) Hg 2+ ) Linear relation among the Hg and Hg in the sample to be measured is calculated 2+ Is a concentration of (3).
(9) According to the method for detecting the mercury ion content by enzyme catalysis colorimetry of the (8), trace heavy metal Hg in urine samples, environmental water, commercial fruit juice beverages and medicament samples 2+ Colorimetric detection was performed and the results are shown in Table 1.
Table 1 trace heavy metal Hg in samples 2+ Detection result (n=5) a
a PB,pH 4.0,
As can be seen from the test results in Table 1, hg in the sample 2+ Recovery rate is between 97.4 and 102.6%, relative error (RSD) is less than 3.7%, which indicates Pd@NiCo as described above 2 O 4 Nanometer enzyme imitation applied to trace heavy metal Hg in urine samples, environmental water, commercial fruit juice beverages and medicament samples 2+ The method has the characteristics of convenience, rapidness, high sensitivity, accurate detection result and the like, and can effectively treat ultra-trace Hg in the sample 2+ And (5) detecting.
The foregoing is illustrative of only a few embodiments of the present invention and is not to be construed as limiting the scope of the invention. It should be noted that modifications, substitutions, improvements, etc. can be made by others skilled in the art without departing from the spirit and scope of the present invention. The scope of the invention should, therefore, be determined with reference to the appended claims.
Claims (9)
1. Pd@NiCo 2 O 4 Application of bifunctional nanometer imitation enzyme, pd@NiCo 2 O 4 The double-function nanometer imitation enzyme comprises NiCo 2 O 4 A substrate and Pd nano particles, wherein the Pd nano particles are tetrahedrons and are loaded on NiCo 2 O 4 The double-function nano enzyme imitation can be applied to detection of trace heavy metal mercury in environmental water, biological and medical samples.
2. The use according to claim 1, wherein the Pd nanoparticles are associated with NiCo 2 O 4 The substrates are connected through metal bond between Pd and Ni and/or Co.
3. The use according to claim 1, wherein said NiCo 2 O 4 The substrate is a two-dimensional sheet structure.
4. Root of Chinese characterThe use according to any one of claims 1 to 3, wherein the Pd nanoparticles have a particle size of between 10 and 15nm, which is dispersed in the NiCo 2 O 4 On the surface of the substrate.
5. The use according to claim 1, characterized in that the pd@nico 2 O 4 The preparation method of the double-function nanometer imitation enzyme comprises the following steps:
(1) Providing a composition containing Co 2+ Ion, ni 2+ Ions, pd 2+ Adding glycol into alkaline mixed solution of ions and polyvinylpyrrolidone, and uniformly mixing to obtain precursor mixed solution;
(2) And (3) treating the precursor mixed solution by microwaves, separating out a solid product after the reaction is finished, and removing a template formed by polyvinylpyrrolidone to obtain the modified polyvinyl pyrrolidone.
6. The method according to claim 5, wherein in step (1), co 2+ Ion source, ni 2+ Ion source, pd 2+ Dispersing an ion source in a neutral polyvinylpyrrolidone solution, uniformly stirring, adding ammonia water and ethylene glycol, and continuously stirring to obtain a precursor mixed solution;
the Co is 2+ The ion source is Co (NO) 3 ) 2 、CoSO 4 、CoCl 2 At least one of (a) and (b);
the Ni is 2+ The ion source is Ni (NO) 3 ) 2 、NiSO 4 、NiCl 2 At least one of (a) and (b);
the Pd is 2+ The ion source is Na 2 PdCl 4 、K 2 PdCl 4 、Pd(CH 3 COO) 2 、PdCl 2 At least one of (a) and (b);
co is dispersed by ultrasonic 2+ Ion source, ni 2+ Ion source, pd 2+ The ion source is dispersed in a neutral polyvinylpyrrolidone solution.
7. The use according to claim 5, wherein step (1)In the above, the Co 2+ Ion, ni 2+ Ions, pd 2+ The proportion of the ions and polyvinylpyrrolidone is (0.2-0.5 mmol): (0.1 to 0.4 mmol): (0.05 to 0.1 mmol): (160-300 mg);
or in the step (1), the alkaline mixed solution is formed by adding ammonia water, and the volume ratio of the ammonia water to the glycol is (100-500 mu L): (10-50 mL), and the concentration of the ammonia water is 25-28%.
8. The use according to claim 5, wherein in step (2), the power of the microwave treatment is 450-700 w and the treatment time is 10-25 min;
or in the step (2), centrifugally separating out a solid product, centrifugally washing the solid product with ethanol and water, and vacuum drying the solid product after the completion of the centrifugal washing to obtain a target product Pd@NiCo 2 O 4 Nanometer enzyme imitation.
9. The use according to claim 1, wherein the method of detection of heavy metal mercury comprises the steps of:
s1, pd@NiCo 2 O 4 Adding colorimetric substrate TMB, disodium hydrogen phosphate-citric acid buffer solution and H into standard solution 2 O 2 Obtaining a sample liquid to be detected;
s2, observing the color change of the liquid to be detected;
in the step S1, the standard solution is Pd@NiCo with the concentration of 0.1mg/mL 2 O 4 A solution;
in step S2, the color change is changed into light blue to dark blue, namely the Hg contained in the sample liquid to be detected 2+ 。
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