CN112844411A - Mercury-promoted two-dimensional graphene oxide stable Ag2S nano mimic enzyme and preparation method and application thereof - Google Patents
Mercury-promoted two-dimensional graphene oxide stable Ag2S nano mimic enzyme and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nano mimic enzyme, in particular to mercury-promoted two-dimensional graphene oxide stabilized Ag2S nanometer mimic enzyme and a preparation method and application thereof. By nano Ag2The strong coordination between the empty d orbit of Ag in S and the lone pair electrons on the oxygen-enriched atom of the graphene oxide is realized by the nano Ag under the condition of ultrasonic dispersion2S is uniformly coordinated and adsorbed on the nano graphene oxide substrate to construct two-dimensional graphene oxide stable Ag2S，Ag2S @ GO. Ag prepared by the invention2S @ GO has strong mercury catalytic oxidase activity, can rapidly catalyze and oxidize TMB to generate blue oxide oxTMB in the presence of trace heavy metal mercury, has strong visual sensitization effect, and catalyzes Michaelis constant (K) by enzymem) And maximum initial velocityRate (V)max) 0.10mM and 3.94X 10mM, respectively‑8M·s‑1. The method can be used for visible colorimetric detection of the content of heavy metal mercury in an environmental water sample, the detection limit can reach nanomolar level, the relative error is less than 3.1%, and the method is simple to operate, high in sensitivity, good in selectivity and strong in visibility.
Description
Technical Field
The invention relates to the technical field of nano mimic enzyme, in particular to mercury-promoted two-dimensional graphene oxide stabilized Ag2S nanometer mimic enzyme and a preparation method and application thereof.
Background
With the rapid development of the industry, great economic benefits are brought, and meanwhile, serious environmental pollution is caused. In which environmental mercury pollution causes great harm to human health. For example, in the 50 s of the 20 th century, water guarantee Bay in Kyushu Japan caused "water guarantee disease", which is the first discovered environmental pollution event caused by mercury pollution, and causes great social harm. Statistically, 5172 people are ill and 730 people are dead in the Japanese water preferentially. In the event of mercury poisoning in 1972, which occurred when irak treated seeds with methylmercury and ethylmercuric fungicides, 459 people died. Thereafter, mercury pollution incidents occur in succession in various countries in the world, which arouses global wide attention, and various measures are taken to prevent mercury pollution.
The mercury pollution has the characteristics of durability, easy migration, high biological enrichment, strong toxicity and the like, and mercury in any form in the environment can be converted into highly toxic methyl mercury under certain conditions, so that great harm is caused to the safety of soil, water and food and the physical and psychological health of citizens. Meanwhile, mercury has long-term cross-border pollution, is listed as a global pollutant by the environmental planning administration of the united nations, is a unique chemical substance which has influence on the global scope except for greenhouse gases, and becomes one of environmental pollutants which are widely concerned in the world.
The nano mimic enzyme is used as an efficient bionic catalyst, has high cost performance and good thermal stability in synthesis and preparation, can catalyze various reactions under mild conditions, has higher selectivity and excellent catalysis efficiency, and is widely applied to the fields of drug synthesis, preparation of drug-assisted materials, photodynamic therapy, bionic catalysis, environmental analysis sensing and the like.
Therefore, there is a need for a highly visible, selective and operable heavy metal Hg2+And (4) analyzing the detection method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing the mercury-promoted two-dimensional graphene oxide stable Ag for colorimetric detection of the content of heavy metal mercury in an environmental water sample, which is simple to operate, high in sensitivity, good in selectivity and strong in visibility2S nanometer mimic enzyme and a preparation method and application thereof.
The technical scheme adopted by the invention for realizing the purpose is as follows: mercury-promoted two-dimensional graphene oxide stable Ag2S nano mimic enzyme by nano Ag2The strong coordination between the empty d orbit of Ag in S and the lone pair electrons on the oxygen-enriched atom of the graphene oxide is realized by the nano Ag under the condition of ultrasonic dispersion2S is uniformly coordinated and adsorbed on the nano graphene oxide substrate to construct two-dimensional graphene oxide stable Ag2S，Ag2S@GO。
The invention also comprises Ag stabilized by mercury-promoted two-dimensional graphene oxide2The preparation method of the S nanometer mimic enzyme comprises the following preparation steps:
(1) mixing AgNO3Placing in a flask, and sequentially adding H2O and graphene oxide;
(2) adding Na dropwise under ultrasonic condition2Reacting the S aqueous solution at room temperature;
(3) centrifugally separating the obtained crude product, fully washing the crude product with deionized water, and drying the crude product in vacuum to obtain the two-dimensional graphene oxide stable Ag2S。
Further, the specific preparation steps are as follows:
(1) 0.55mmol, 210mg AgNO are weighed3Placing in a round bottom flask, and sequentially adding 30.0mL of H2O and 9.0mL, 30mg/mL graphene oxide;
(2) under the ultrasonic condition, 15mL of 0.075mol/L Na is added dropwise2Reacting the S aqueous solution at room temperature for 0.5h, centrifugally separating a crude product at 6000r/min, fully washing the crude product with deionized water, and drying the crude product in vacuum to obtain the two-dimensional graphene oxide stable Ag2S。
The invention also comprises Ag stabilized by mercury-promoted two-dimensional graphene oxide2Application of S nano mimic enzyme, and two-dimensional graphene oxide stabilized Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+Carrying out naked eye sensing visual detection or Hg2+The content of (A) is detected by colorimetry.
Further, the detection mechanism is as follows:
Ag2s @ GO has no nano enzyme activity, and has high-efficiency oxidation-simulated enzyme activity in the presence of mercury; due to Hg2+Has strong coordination with S element, and can separate S element from nano Ag2The S is extracted, the strong catalytic action of the nano-silver is recovered, and the colorimetric substrate TMB can be oxidized to generate blue oxTMB in the presence of oxygen. Meanwhile, the ultrathin two-dimensional graphene oxide has larger specific surface area, more oxygen-rich groups (such as hydroxyl, carboxyl epoxy and the like), good biocompatibility, no toxicity, no pollution and the like, can enhance the environmental compatibility, reduce the toxicity of the sensing material, and improve the toxicity Hg of the sensing material2+Enriching the adsorption capacity.
Further, the two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+The method comprises the following specific steps of carrying out naked eye sensing visual detection:
(1) preparing Ag2S @ GO standard solution and Hg2+A standard solution;
(2) preparation of environmental samples
Randomly measuring 1 part of each water sample in different environments, filtering for three times by a 4.5-micron microporous filtering membrane, and removing suspended matters;
(3) heavy metal Hg in sample2+Performing naked eye sensing visual detection
Remove 600. mu.L of 0.1mg/mL Ag2S @ GO standard solution was placed in a centrifuge tube and 200. mu.L of 1.5mM TMB and various volumes of 4.0mmol/L Hg were added2+Diluting the standard solution or sample to be tested to 3mL with pH4.0 disodium hydrogen phosphate-citric acid buffer solution, mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and observingThe color of the solution was observed to change.
Further, the Ag2The preparation steps of the S @ GO standard solution are as follows: 0.01g of dried Ag was weighed2S @ GO is dispersed into 100mL of purified water under the ultrasonic action to prepare Ag with the concentration of 0.1mg/mL2S @ GO standard solution.
Further, the two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+The specific preparation steps for colorimetric detection of the content are as follows:
taking 600 mu L of Ag with the concentration of 0.1mg/mL2S @ GO standard solution, 4.0mmol L in different volumes -1200 mu L of 1.5mM TMB, adding disodium hydrogen phosphate-citric acid buffer solution with pH of 4.0 to make the volume to 3mL, mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and substituting the absorption intensity value into A652＝0.00822+0.00576 cHg 2+(R20.9968) linear range of 0 to 180.0 × 10-8M cHg 2+And calculating Hg in the sample to be measured2+The concentration of (c).
Further, the optimal detection conditions are as follows: ag2The volume concentration of S @ GO is 600 mu L and 0.1 mg/mL; the reaction pH value is 4.0; the reaction temperature is 25 ℃; c. CTMB0.05 mM; the reaction time was 30 min.
Further, the Ag2The S @ GO-TMB reaction system has specific selective spectral response to heavy metal mercury, and is accompanied by visible colorless to blue hyperchromic effect, and enzyme catalysis Michaelis constant (K)m) And maximum initial rate (V)max) 0.10mM and 3.94X 10mM, respectively-8M·s-1。
The mercury-promoted two-dimensional graphene oxide stabilized Ag2The S nano mimic enzyme and the preparation method and the application thereof have the beneficial effects that:
the invention provides mercury-promoted two-dimensional graphene oxide stabilized Ag2Ag constituted by S nano mimic enzyme2S nanoparticles are uniformly distributed, Ag2S @ GO is high in stability, mercury promotes Ag2High catalytic activity of S @ GO nano oxidase and corresponding color enhancementThe method has the advantages of high sensitivity and good reproducibility for colorimetric identification of heavy metal mercury ions; wide linear range (0-180.0X 10)-8M cHg 2+) Detection limit of damol (9.8X 10)-9M), which is much lower than 3.0X 10 regulated by the International health organization-8mol·L-1The drinking water has the advantages of healthy standard of mercury ions, strong visibility and simple and convenient operation.
Drawings
FIG. 1 shows two-dimensional graphene oxide stabilized Ag2S nanometer mimic enzyme to Hg2+Schematic diagram of reaction structure for detection;
in the context of figure 2, it is shown,
a)Ag2TEM and HR-TEM images of S @ GO;
b)Ag2nano Ag in S @ GO2S particle size distribution map;
c)Ag2s @ GO material C element distribution mirror image;
d)Ag2s element distribution mirror image in S @ GO material;
e)Ag2an Ag element distribution mirror image in the S @ GO material;
in the context of figure 3, it is shown,
a) different systems GO + TMB, GO + Hg2++TMB,Ag2S@GO+TMB,Ag2S@GO+Hg2++TMB,Hg2+Comparison of ultraviolet spectra and colors of + TMB and TMB;
b) fig. 2a) time resolved contrast plot of absorption intensity at pH4.0, 652nm for different systems;
in the context of figure 4, it is shown,
a) promoting Ag to mercury with different pH values2Influence graph of S @ GO nanoenzyme activity;
b) promoting Ag to mercury at different temperatures2Influence graph of S @ GO nanoenzyme activity;
c) promoting Ag to mercury with different concentrations of TMB2Influence graph of S @ GO nanoenzyme activity;
d) promoting Ag to mercury with different reaction time2Influence graph of S @ GO nanoenzyme activity;
in the context of figure 5, it is shown,
a) mercury promoted Ag at different TMB concentrations2A reaction rate profile of S @ GO nanoenzyme activity;
b) mercury promoted Ag at different TMB concentrations2A linear relationship graph of reaction rate of S @ GO nanoenzyme activity;
c) promoting Ag to mercury in presence of oxygen and nitrogen2(ii) S @ GO nano-enzyme activity spectrum and colorimetric influence diagram;
d) verification spectrogram of oxidase activity mechanism (600 mu L of 0.1mg/mL Ag2S@GO,pH＝4.0)；
In the context of figure 6, it is shown,
a) promoting Ag by mercury with different interfering ions2Influence graphs of spectral performance and colorimetric performance of S @ GO nanoenzyme activity (from bottom to top, blank and K are sequentially shown in the figure+,Ca2+,Ba2+,Zn2+,Cd2+,Fe2+,Bi3+,Ni2+,Pb2+,Fe3+,Mn2+,Cr3+,Ag+,Cu2+,Co2+And Hg2+，cIon(s)＝10.0μM,cHg 2+＝1.0μM)；
b) Different interfering ions and Hg2+Promoting Ag to mercury when coexisting2(ii) an influence plot of spectral properties of S @ GO nanoenzyme activity;
in the context of figure 7 of the drawings,
a) colorimetric sensing of heavy metal Hg2+The concentration of mercury ions is 0,1.0,5.0,10.0,20.0,40.0,60.0 and 80.0,100.0,120.0,140.0,160.0,180.0 multiplied by 10 in turn- 8M)；
b) Light absorption intensity (A)652) And concentration of mercury ions (c)Hg 2+) Linear relationship between (200. mu.L of 1.5mM TMB, 600. mu.L of 0.1mg/mL Ag2S@GO,pH＝4.0)。
Detailed Description
The invention is further explained in detail with reference to the drawings and the specific embodiments;
example 1:
mercury-promoted two-dimensional graphene oxide stable Ag2S nano mimic enzyme by nano Ag2In the S, the strong coordination between the empty d orbit of Ag and the lone pair electrons on the oxygen-enriched atom of the graphene oxide disperses in the ultrasonicUnder the condition, nano Ag2S is uniformly coordinated and adsorbed on the nano graphene oxide substrate to construct two-dimensional graphene oxide stable Ag2S，Ag2S@GO。
The invention also comprises Ag stabilized by mercury-promoted two-dimensional graphene oxide2The preparation method of the S nanometer mimic enzyme comprises the following preparation steps:
(1) mixing AgNO3Placing in a flask, and sequentially adding H2O and graphene oxide;
(2) adding Na dropwise under ultrasonic condition2Reacting the S aqueous solution at room temperature;
(3) centrifugally separating the obtained crude product, fully washing the crude product with deionized water, and drying the crude product in vacuum to obtain the two-dimensional graphene oxide stable Ag2S。
The preparation method comprises the following specific steps:
(1) 0.55mmol, 210mg AgNO are weighed3Placing in a round bottom flask, and sequentially adding 30.0mL of H2O and 9.0mL, 30mg/mL graphene oxide;
(2) under the ultrasonic condition, 15mL of 0.075mol/L Na is added dropwise2Reacting the S aqueous solution at room temperature for 0.5h, centrifugally separating a crude product at 6000r/min, fully washing the crude product with deionized water, and drying the crude product in vacuum to obtain the two-dimensional graphene oxide stable Ag2S。
The invention also comprises Ag stabilized by mercury-promoted two-dimensional graphene oxide2Application of S nano mimic enzyme, and two-dimensional graphene oxide stabilized Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+Carrying out naked eye sensing visual detection or Hg2+The content of (A) is detected by colorimetry.
As shown in fig. 1, the detection mechanism is:
Ag2s @ GO has no nano enzyme activity, and has high-efficiency oxidation-simulated enzyme activity in the presence of mercury, Hg2+Has strong coordination with S element, and can separate S element from nano Ag2The S is extracted, the strong catalytic action of the nano-silver is recovered, the colorimetric substrate TMB can be oxidized to generate blue oxTMB in the presence of oxygen, and meanwhile, the ultrathin two-dimensional graphene oxide has the advantages ofLarger specific surface area, more oxygen-rich groups (such as hydroxyl, carboxyl epoxy and the like), good biocompatibility, no toxicity, no pollution and the like, can enhance the environmental compatibility, reduce the toxicity of the sensing material, and can improve the toxicity Hg of the sensing material2+Enriching the adsorption capacity.
The two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+The method comprises the following specific steps of carrying out naked eye sensing visual detection:
(1) preparing Ag2S @ GO standard solution and Hg2+A standard solution;
(2) preparation of environmental samples
Randomly measuring 1 part of each water sample in different environments, filtering for three times by a 4.5-micron microporous filtering membrane, and removing suspended matters;
(3) heavy metal Hg in sample2+Performing naked eye sensing visual detection
Remove 600. mu.L of 0.1mg/mL Ag2S @ GO standard solution was placed in a centrifuge tube and 200. mu.L of 1.5mM TMB and various volumes of 4.0mmol/L Hg were added2+And (3) metering the volume of the standard solution or the sample to be detected to 3mL by using a pH (4.0) disodium hydrogen phosphate-citric acid buffer solution, uniformly mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and observing the change of the color of the solution.
The Ag is2The preparation steps of the S @ GO standard solution are as follows: 0.01g of dried Ag was weighed2S @ GO is dispersed into 100mL of purified water under the ultrasonic action to prepare Ag with the concentration of 0.1mg/mL2S @ GO standard solution.
The two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+The specific preparation steps for colorimetric detection of the content are as follows:
taking 600 mu L of Ag with the concentration of 0.1mg/mL2S @ GO standard solution, 4.0mmol L in different volumes -1200 mu L of 1.5mM TMB, adding disodium hydrogen phosphate-citric acid buffer solution with pH of 4.0 to make the volume to 3mL, mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and adjusting the absorption intensityValue into A652＝0.00822+0.00576 cHg 2+(R20.9968) linear range of 0 to 180.0 × 10-8M cHg 2+And calculating Hg in the sample to be measured2+The concentration of (c).
The optimal detection conditions are as follows: ag2The volume concentration of S @ GO is 600 mu L and 0.1 mg/mL; the reaction pH value is 4.0; the reaction temperature is 25 ℃; c. CTMB0.05 mM; the reaction time was 30 min.
The Ag is2The S @ GO-TMB reaction system has specific selective spectral response to heavy metal mercury, and is accompanied by visible colorless to blue hyperchromic effect, and enzyme catalysis Michaelis constant (K)m) And maximum initial rate (V)max) 0.10mM and 3.94X 10mM, respectively-8M·s-1。
Ag2S @ GO has strong mercury catalytic oxidation enzyme activity, and can rapidly catalyze and oxidize conventional colorimetric substrates 3,3 in the presence of trace heavy metal mercury’,5,5’The (TMB) generates blue oxigen oxTMB with strong visual sensitization effect, and the enzyme catalyzes Michaelis constant (K)m) And maximum initial rate (V)max) 0.10mM and 3.94X 10mM, respectively-8M·s-1. Under optimized conditions (pH4.0,25 ℃,600 μ L0.1 mg/mL Ag2S @ GO and 30min), Ag2S @ GO is successfully applied to visible colorimetric detection of heavy metal mercury content in an environmental water sample, and the detection limit can reach nanomolar level (9.8 multiplied by 10)–9mol/L), relative error is less than 3.1%, operation is simple, sensitivity is high, selectivity is good, and visibility is strong.
Example 2:
mercury-promoted two-dimensional graphene oxide stable Ag2The S nanometer mimic enzyme and the preparation method and the application thereof are as follows:
(1) one-step ultrasonic-assisted method for preparing two-dimensional graphene oxide stable Ag2S(Ag2S@GO)
210mg (0.55mmol) of AgNO are weighed out3Placing in a 100mL round-bottom flask, and sequentially adding 30.0mL of H2O and 9.0mL (30mg/mL) of graphene oxide, and under the ultrasonic condition, dropwise adding 15mL (0.075mol/L) of Na2Aqueous solution of SReacting at room temperature for 0.5h, centrifuging the crude product at 6000r/min, fully washing with deionized water, and drying in vacuum to obtain the target two-dimensional graphene oxide stable Ag2S(Ag2S@GO)。
Target Ag2The structure of S @ GO is characterized by means of TEM, HR-TEM, particle size distribution, element analysis and the like, as shown in figure 2. Formed Ag2The particle size of the S nano particles is concentrated to about 37nm and is uniformly dispersed on the bottom surface of the two-dimensional graphene oxide base.
(2)Ag2Preparation of S @ GO standard solution
0.01g of dried Ag was weighed2S @ GO is dispersed into 100mL of purified water under the ultrasonic action to prepare Ag with the concentration of 0.1mg/mL2S @ GO standard solution, and storing at room temperature for later use;
(3)Hg2+preparation of Standard solutions
0.2715g (2.0mmol) of mercuric chloride is weighed and dissolved in 250.0mL of purified water to prepare 4.0mmol L-1The standard solution of mercury ions is stored at room temperature for later use;
(4) preparation of environmental samples
Randomly measuring 1000.0mL of each of environmental water samples such as Yihe water, campus underground water, tap water and the like by 1 part, filtering the environmental water samples for three times by a 4.5-micron microporous filtering membrane, removing suspended matters, and storing the environmental water samples at room temperature for later use;
(5) mercury promoting Ag2Study on activity of S @ GO nano mimic enzyme
Remove exactly 600. mu.L (0.1mg/mL) of Ag2S @ GO standard solution was placed in a 5mL centrifuge tube and 200. mu.L (1.5mM) TMB and 20.0. mu.L Hg were added2+And (3) metering the volume of the standard solution to 3mL by using a disodium hydrogen phosphate-citric acid buffer solution with the pH value of 4.0, uniformly mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and observing the color change of the solution.
The enzymatic reaction mechanism is verified to be an oxidase reaction mechanism, and FIGS. 3-5 show that the pH, temperature, TMB concentration and reaction time are different for promoting Ag to mercury2Influence of S @ GO nano-enzyme activity to determine optimal mercury-promoted Ag2The external conditions of the activity of the S @ GO nano-mimic enzyme are as follows: 20 μ L of 0.15mM Hg2+,200μL 1.5mM TMB,600μL 0.1mg/mL Ag2S @ GO, pH4.0, reaction for 30min at room temperature, enzyme catalyzed Michaelis constant (K)m) And maximum initial rate (V)max) 0.10mM and 3.94X 10mM, respectively-8M·s-1。
(6) Colorimetric detection method for mercury ion content
FIG. 6 shows that the metal ions in the common environment promote Ag to mercury2The influence of S @ GO nano-enzyme activity has extremely strong selectivity. On the basis, 600 mu L (0.1mg/mL) of Ag is taken under the optimized experimental conditions2S @ GO standard solution is put into a 5mL centrifuge tube, and 4.0mmol L of different volumes is added-1200 μ L (1.5mM) of TMB, adding 3mL of disodium hydrogen phosphate-citric acid buffer solution with pH4.0, mixing uniformly, standing at room temperature for 30min, measuring the absorption spectrum of the system, and drawing a linear ratio relationship between the absorption spectrum intensity and the heavy metal mercury concentration as shown in fig. 7: a. the652＝0.00822+0.00576cHg 2+Linear range of 0 to 180.0X 10-8M cHg 2+Coefficient of correlation (R)2) 0.9968, detection limit 9.8X 10-9M (S/N ═ 3), which is much lower than 3.0X 10 regulated by the International organization for health-8mol·L-1Drinking water mercury ion health standard.
In the linear range of 0-180.0X 10-8M cHg 2+According to the obtained linear regression equation A652＝0.00822+0.00576 cHg 2+The method is successfully applied to the detection of mercury ions in bare holes of environmental water samples such as Yihe river water, campus underground water and tap water, and the results are shown in table 1. Hg in the sample2+The recovery rate is between 98.6 and 100.8 percent, and the relative error (RSD) is less than 3.1 percent.
TABLE 1 Hg in different samples of environmental water2+Test results (n ═ 5)a
apH 4.0,cAg2S@GO＝20μg/mL
bThe actual content of mercury ions in the sample is found in the table multiplied by 10-2(the sample was concentrated 100-fold before testing).
The ultrasonic-assisted synthesis method can lead the generated nano Ag to be2S is dispersed and adsorbed on the graphene substrate more uniformly; discussion of mercury-promoted stabilization of Ag by two-dimensional graphene oxide2S nanometer simulates enzyme activity, influence factor, activity mechanism and Hg in environmental sample2+The application research such as naked eye detection and the like is successfully applied to Hg in a water sample2+Visibility sensing. The method has the advantages of simple and rapid operation, good selectivity, high sensitivity and the like, and can rapidly treat heavy metal Hg in environmental samples (such as Yihe water, campus groundwater, tap water and the like)2+The method is fast and efficient naked eye sensing.
The optimal test conditions were determined to be: 600 μ L of 0.1mg/mL Ag2S@GO，pH＝4.0，25℃，cTMBReaction time 30min, 0.05 mM. Common coexisting ions, e.g. K+,Ca2+,Ba2+,Zn2+,Cd2+,Fe2+,Bi3+,Ni2+,Pb2+,Fe3+,Mn2+,Cr3+,Ag+,Cu2+,Co2+Equal pair of Hg2+The colorimetric sensing of (2) has no obvious interference. The absorption spectrum intensity has a special linear ratio relation to the heavy metal mercury concentration: a. the652＝0.00822+0.00576 cHg 2+Linear range of 0 to 180.0X 10-8M cHg 2+Coefficient of correlation (R)2) 0.9968, detection limit 9.8X 10-9M (S/N-3), Hg in the sample2+The recovery rate is between 98.6 and 100.8 percent, and the relative error (RSD) is less than 3.1 percent.
Ag2S @ GO has no nano enzyme activity, and has high-efficiency oxidation-simulated enzyme activity in the presence of mercury, Hg2+Has strong coordination with S element, and can separate S element from nano Ag2The S is extracted, the strong catalytic action of the nano-silver is recovered, the colorimetric substrate TMB can be oxidized to generate blue oxTMB in the presence of oxygen, and meanwhile, the ultrathin two-dimensional graphene oxide has large specific surface area and hydrophilicity and can pass physicalActing to convert Hg2+The graphene oxide is enriched on the surface, and in addition, the graphene oxide also has more oxygen-rich groups (such as hydroxyl, carboxyl epoxy and the like), and Hg enriched on the surface of the graphene oxide can be enriched through chemical action2+Firmly locked and physically and chemically synergistic effect of mercury on promoting two-dimensional graphene oxide to stabilize Ag2The S nanometer mimic enzyme has good activity and high sensitivity, and the two-dimensional graphene oxide also has good biocompatibility, is non-toxic and pollution-free, and the like, and can enhance the environmental compatibility and reduce the toxicity of sensing materials.
The experimental methods used in the above examples are all conventional methods unless otherwise specified.
The materials and reagents used in the above examples were commercially available or synthesized from commercially available raw materials, unless otherwise specified.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (10)
1. Mercury-promoted two-dimensional graphene oxide stable Ag2The S nanometer mimic enzyme is characterized in that: by nano Ag2The strong coordination between the empty d orbit of Ag in S and the lone pair electrons on the oxygen-enriched atom of the graphene oxide is realized by the nano Ag under the condition of ultrasonic dispersion2S is uniformly coordinated and adsorbed on the nano graphene oxide substrate to construct two-dimensional graphene oxide stable Ag2S，Ag2S@GO。
2. Preparation of mercury-promoted two-dimensional graphene oxide stabilized Ag according to claim 12The method for simulating the enzyme S nanometer is characterized by comprising the following preparation steps:
(1) mixing AgNO3Placing in a flask, and sequentially adding H2O and graphene oxide;
(2) adding Na dropwise under ultrasonic condition2Dissolving S in waterReacting at room temperature;
(3) centrifugally separating the obtained crude product, fully washing the crude product with deionized water, and drying the crude product in vacuum to obtain the two-dimensional graphene oxide stable Ag2S。
3. The mercury-promoted two-dimensional graphene oxide stabilized Ag of claim 22The method for simulating the enzyme by the S nanometer is characterized by comprising the following steps: the preparation method comprises the following specific steps:
(1) 0.55mmol, 210mg AgNO are weighed3Placing in a round bottom flask, sequentially adding 30.0mLH2O and 9.0mL, 30mg/mL graphene oxide;
(2) under ultrasonic conditions, 15mL of 0.075mol/LNa is added dropwise2Reacting the S aqueous solution at room temperature for 0.5h, centrifugally separating a crude product at 6000r/min, fully washing the crude product with deionized water, and drying the crude product in vacuum to obtain the two-dimensional graphene oxide stable Ag2S。
4. Mercury-promoted two-dimensional graphene oxide stable Ag2Application of S nano mimic enzyme, and two-dimensional graphene oxide stabilized Ag2S has the structure of claim 1 or is prepared by the method of any one of claims 2-3, wherein:
the two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+Carrying out naked eye sensing visual detection or Hg2+The content of (A) is detected by colorimetry.
5. Use according to claim 4, characterized in that the detection mechanism is:
Ag2s @ GO has no nano enzyme activity, and has high-efficiency oxidation-simulated enzyme activity in the presence of mercury, Hg2+Has strong coordination with S element, and can separate S element from nano Ag2The S is extracted, the strong catalytic action of the nano-silver is recovered, and the colorimetric substrate TMB can be oxidized to generate blue oxTMB in the presence of oxygen.
6. According to claim4, characterized in that the two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+The method comprises the following specific steps of carrying out naked eye sensing visual detection:
(1) preparing Ag2S @ GO standard solution and Hg2+A standard solution;
(2) preparation of environmental samples
Randomly measuring 1 part of each water sample in different environments, filtering for three times by a 4.5-micron microporous filtering membrane, and removing suspended matters;
(3) heavy metal Hg in sample2+Performing naked eye sensing visual detection
Remove 600. mu.L of 0.1mg/mL Ag2S @ GO standard solution was placed in a centrifuge tube and 200. mu.L of 1.5mM TMB and various volumes of 4.0mmol/L Hg were added2+And (3) metering the volume of the standard solution or the sample to be detected to 3mL by using a pH (4.0) disodium hydrogen phosphate-citric acid buffer solution, uniformly mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and observing the change of the color of the solution.
7. Use according to claim 6, wherein the Ag is2The preparation steps of the S @ GO standard solution are as follows: 0.01g of dried Ag was weighed2S @ GO is dispersed into 100mL of purified water under the ultrasonic action to prepare Ag with the concentration of 0.1mg/mL2S @ GO standard solution.
8. Use according to claim 4, wherein the two-dimensional graphene oxide stabilizes Ag2Application of S nano mimic enzyme in heavy metal Hg in environmental sample2+The specific preparation steps for colorimetric detection of the content are as follows:
taking 600 mu L of Ag with the concentration of 0.1mg/mL2S @ GO standard solution, 4.0mmol L in different volumes-1200 mu L of 1.5mM TMB, adding disodium hydrogen phosphate-citric acid buffer solution with pH of 4.0 to make the volume to 3mL, mixing, standing at room temperature for 30min, measuring the absorption spectrum of the system, and substituting the absorption intensity value into A652＝0.00822+0.00576cHg 2+(R20.9968) linear range of 0 to 180.0 × 10-8M cHg 2+And calculating Hg in the sample to be measured2+The concentration of (c).
9. Use according to claim 8, characterized in that: the optimal detection conditions are as follows: ag2The volume concentration of S @ GO is 600 mu L and 0.1 mg/mL; the reaction pH value is 4.0; the reaction temperature is 25 ℃; c. CTMB0.05 mM; the reaction time was 30 min.
10. Use according to any one of claims 5 or 8, characterized in that: the Ag is2The S @ GO and TMB reaction system has specific selective spectral response to heavy metal mercury, and is accompanied by visible colorless to blue hyperchromic effect, and enzyme catalysis Michaelis constant (K)m) And maximum initial rate (V)max) 0.10mM and 3.94X 10mM, respectively-8M·s-1。
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