CN114632547A - Preparation method and application of two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material - Google Patents

Preparation method and application of two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material Download PDF

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CN114632547A
CN114632547A CN202210175222.1A CN202210175222A CN114632547A CN 114632547 A CN114632547 A CN 114632547A CN 202210175222 A CN202210175222 A CN 202210175222A CN 114632547 A CN114632547 A CN 114632547A
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hhtp
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孙义民
黄威
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Wuhan Institute of Technology
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Abstract

The invention provides a preparation method and application of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material. The method adopts a surfactant and an ultrasonic-assisted liquid phase stripping strategy to synthesize the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs, and then utilizes a solvothermal method to reduce HAuCl4 in situ to obtain Au-NPs/Cu-doped particles loaded with gold nanoparticlesHHTP-NSs double nano enzyme; the peroxidase-like activity of the nano enzyme is proved by using 3,3',5,5' -Tetramethylbenzidine (TMB) as a color developing agent; the Au-NPs/Cu-HHTP-NSs nanoenzyme modified glassy carbon electrode GCE is obtained by drop coating, is used as a working electrode for electrocatalysis and reduction of added hydrogen peroxide, and shows obvious enhancement of reduction peak signals along with the increase of the concentration of the hydrogen peroxide, so that a ratio electrochemical sensor is constructed for high-sensitivity H2O2And (6) detecting.

Description

Preparation method and application of two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material, a method for preparing a double-nanoenzyme-based electrochemical sensor by adopting the composite material, and application of the obtained double-nanoenzyme-based electrochemical sensor in hydrogen peroxide sensing detection in cancer cells.
Background
Metal Organic Frameworks (MOFs) are porous organic-inorganic hybrid materials having a periodic network structure constructed by metal ions or metal clusters and organic ligands through coordination bonds. To date, great progress has been made in the development of electrochemical sensing platforms based on MOF nanoenzymes for biosensing of small biological molecules, neurotransmitters, RNA, etc. This is due to the accurate recognition of active sites based on uniform distribution on the atomic scale in MOF nanoenzymes, which helps to elucidate the catalytic mechanism and provides good insight for designing more efficient catalytic systems. However, the vast majority of these MOF nanoenzymes are three-dimensional (3D) MOF crystals, with all coordinated saturated metal sites buried by organic ligands. At the same time, 3D MOFs also exhibit very low electronic conductivity, even insulators, because of their insulating and redox-inert bridging ligands. Therefore, the improvement of the conductivity of the MOF-based nanoenzyme is of great significance to the application in the fields of electrochemical catalysis and sensing.
In 2012, the Yaghi group first published a first article on Chemistry of materials on two-dimensional conductive MOF (2D c-MOF) materials, followed by the emergence of novel 2D c-MOFs of various structures and functionalities. This makes 2D c-MOF a new research direction. From a planar square coordination mode (e.g. metal-O)4metal-S4Metal- (NH)4) 2D c-MOFs constructed with planar conjugated organic ligands have a highly delocalized pi-electron structure, which increases in-plane charge transport and confers excellent charge mobility to 2D c-MOF. However, most 2D c-MOFs synthesized by traditional solvothermal methods are bulk powders, and most of the active sites are hidden in the framework, which results in low utilization rate of the internal active metal center and slow reaction kinetics, and simultaneously, is not easy to introduce external functional substances for directly constructing 2D c-MOF nano-MOFsRice composite materials, further providing new functions and possibilities. This greatly limits the application of 2D c-MOF in electrochemical catalysis and sensing.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material, which is characterized in that an ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs is synthesized by adopting a surfactant and an ultrasonic-assisted liquid phase stripping strategy, and HAuCl is reduced in situ by utilizing a solvothermal method4The Au-NPs/Cu-HHTP-NSs composite material loaded with the gold nanoparticles, namely Au-NPs/Cu-HHTP-NSs double nanoenzyme, is obtained, so that the problems that the existing MOFs material is poor in conductivity, low in utilization rate of an internal active metal center, slow in reaction kinetics, not easy to introduce external functional substances and the like are solved.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material comprises the following steps:
1) preparing ultrathin two-dimensional conductive MOF nanosheets Cu-HHTP-NSs by adopting a surfactant-assisted method and an ultrasonic stripping method;
2) ultrasonically dispersing the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs obtained in the step 1) in an ethanol solution to prepare a Cu-HHTP-NSs nanosheet dispersion liquid with a certain concentration;
3) adding HAuCl with a certain concentration into the Cu-HHTP-NSs nanosheet dispersion liquid obtained in the step 2)4Solution of HAuCl by in-situ reduction4Reducing the metal nano particles into gold nano particles, cooling to room temperature, centrifuging, and freeze-drying to obtain the two-dimensional conductive MOF nano sheet loaded gold nano particle composite material.
Optionally, the thickness of the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs in step 1) is 2-10 nm.
Optionally, the concentration of the Cu-HHTP-NSs nanosheet dispersion in step 2) is 0.1-1 g/L.
Optionally, the two-dimensional conductive MOF nanosheet-loaded gold nanoparticle composite material in step 3) is synthesized by the following method:
s1: measuring 500-1000mL of Cu-HHTP-NSs nanosheet dispersion obtained in the step 2), and violently stirring at the rotating speed of 800-1000 r.p.m;
s2: slowly dropwise adding 0.25mL-1mL of 1mol/L HAuCl into the dispersion liquid of the step S14After the solution is dissolved, continuously stirring for 20-60min to obtain a mixed solution A;
s3: and (4) placing the mixed solution A obtained in the step S2 at 40-60 ℃ for in-situ reduction reaction, cooling to room temperature after reacting for 3-5 hours, centrifuging, and freeze-drying to obtain the two-dimensional conductive MOF nanosheet-loaded gold nanoparticle composite material.
Optionally, the average particle size of gold nanoparticles in the two-dimensional conductive MOF nanosheet supported gold nanoparticle composite material of step 3) is 2-10 nm.
The second purpose of the invention is to provide a preparation method of a double nano enzyme-based electrochemical sensor, which comprises the following steps:
1) transferring the two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material prepared by the preparation method onto a glassy carbon electrode GCE to form an Au-NPs/Cu-HHTP-NSs/GCE modified electrode;
2) inserting the Au-NPs/Cu-HHTP-NSs/GCE modified electrode serving as a working electrode into an electrolytic cell, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, taking 0.1M phosphoric acid buffer solution PBS as electrolyte, measuring an amperometric timing-current response curve of different hydrogen peroxide concentrations by adopting a timing current method, fitting a linear relation between the hydrogen peroxide concentration and corresponding current, and constructing a ratiometric electrochemical sensor based on the sensing interface of the Au-NPs/Cu-HHTP-NSs/GCE modified electrode, namely a double-nanoenzyme-based electrochemical sensor.
The third purpose of the invention is to provide an application of the double nano enzyme-based electrochemical sensor prepared by the preparation method in hydrogen peroxide sensing detection in cancer cells.
Compared with the prior art, the preparation method of the two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material has the following advantages:
1. the inventionFirstly, preparing ultrathin 2D c-MOF nanosheet Cu-HHTP-NSs, then ultrasonically dispersing the ultrathin 2D c-MOF nanosheet Cu-HHTP-NSs in an ethanol solution, and reducing HAuCl in situ by adopting a solvothermal method4The Au-NPs/Cu-HHTP-NSs composite material is obtained. The composite material still maintains the ultrathin morphology of the substrate Cu-HHTP-NSs, and the loaded gold nanoparticles have the average particle size of about 2-10nm and are highly dispersed on the surface of the Cu-HHTP-NSs. The adopted solvothermal in-situ reduction method does not need to additionally add a strong reducing agent and a blocking agent, avoids the damage of the strong reducing agent to the MOF structure, and solves the problem that the noble metal nanoparticles with small size and regular appearance are difficult to synthesize in situ on the ultrathin two-dimensional conductive MOF by a simple and mild method.
2. The Au-NPs/Cu-HHTP-NSs prepared by the invention has good enzyme-like activity in H2O2And 3,3',5,5' -Tetramethylbenzidine (TMB), H can be reacted2O2The catalytic decomposition into OH, the resulting OH further oxidizes the leuco enzyme substrate TMB to a blue product, the oxidation state of TMB (oxTMB). In the UV-Vis test, oxTMB has obvious absorbance at 652nm, and Au-NPs/Cu-HHTP-NSs obtained by the synergistic effect of the double nano-enzyme activities of Cu-HHTP-NSs and Au-NPs show high peroxidase-like (POD) activity.
3. The Au-NPs/Cu-HHTP-NSs prepared by the method has good electrocatalysis performance, can be transferred to a glassy carbon electrode to be made into an Au-NPs/Cu-HHTP-NSs/GCE modified electrode, and the ratiometric electrochemical sensor based on the sensing interface of the Au-NPs/Cu-HHTP-NSs/GCE modified electrode is constructed and used for detecting hydrogen peroxide with high sensitivity and specificity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation of the invention. In the drawings:
FIG. 1 is a topographical view of an Au-NPs/Cu-HHTP-NSs composite material prepared in example 1 of the present invention, wherein FIG. 1A is an Atomic Force Microscope (AFM) spectrum of Cu-HHTP-NSs; FIG. 1B is a Scanning Electron Microscope (SEM) spectrum of Cu-HHTP-NSs; FIG. 1C is a Transmission Electron Microscope (TEM) spectrum of Cu-HHTP-NSs; FIG. 1D is a Transmission Electron Microscope (TEM) spectrum of Au-NPs/Cu-HHTP-NSs; FIG. 1E is a Transmission Electron Microscope (TEM) micrograph of higher magnification Au-NPs/Cu-HHTP-NSs; FIG. 1F is a Scanning Electron Microscope (SEM) spectrum of bulk Cu-HHTP-bulk;
FIG. 2 is a diagram of X-ray photoelectron spectroscopy (XPS) of Cu-HHTP-NSs and Au-NPs/Cu-HHTP-NSs prepared in example 1 of the present invention, wherein FIG. 2A is a full spectrum diagram of Cu-HHTP-NSs and Au-NPs/Cu-HHTP-NSs prepared; FIG. 2B is a C1s spectrum of prepared Cu-HHTP-NSs and Au-NPs/Cu-HHTP-NSs; FIG. 2C is a Cu 2p spectrum of prepared Cu-HHTP-NSs and Au-NPs/Cu-HHTP-NSs; FIG. 2D is the Au 4f spectrum of Au-NPs/Cu-HHTP-NSs prepared according to the present invention;
FIG. 3 is a graph showing the effect of peroxidase activity of different nanoenzymes prepared in example 1 of the present invention;
FIG. 4 is a cyclic voltammogram of Au-NPs/Cu-HHTP-NSs/GCE electrodes prepared in example 2 of the present invention in PBS (pH 7.3) buffer containing 0.5mM, 1mM, 2mM, 3mM, 4mM, and 5mM hydrogen peroxide;
FIG. 5 is a graph of the timed current response of Au-NPs/Cu-HHTP-NSs/GCE electrodes prepared in example 2 of the present invention to relatively low hydrogen peroxide concentrations in PBS (pH 7.3) buffer;
FIG. 6 is a graph of the timed current response of Au-NPs/Cu-HHTP-NSs/GCE electrode prepared in example 2 of the present invention to relatively high hydrogen peroxide concentrations in PBS (pH 7.3) buffer solution;
FIG. 7 is a schematic diagram of the Au-NPs/Cu-HHTP-NSs composite material of the invention used for preparing an electrochemical sensor and carrying out hydrogen peroxide sensing detection in cancer cells.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and example 1.
A preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material comprises the following steps:
1) preparing 3.6nm ultrathin two-dimensional conductive MOF nanosheets Cu-HHTP-NSs by adopting a surfactant-assisted method and an ultrasonic stripping method, wherein AFM, SEM and TEM spectrograms of the Cu-HHTP-NSs are respectively shown in figures 1A, 1B and 1C, and the SEM spectrogram of the Cu-HHTP-bulk obtained by a direct solvothermal method without adding a surfactant is shown in figure 1F;
2) ultrasonically dispersing the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs obtained in the step 1) in an ethanol solution to prepare a Cu-HHTP-NSs nanosheet dispersion liquid with the concentration of 1 g/L;
3) adding HAuCl with a certain concentration into the Cu-HHTP-NSs nanosheet dispersion liquid obtained in the step 2)4Solution of HAuCl by in-situ reduction4Reducing the metal nano particles into gold nano particles, cooling the gold nano particles to room temperature, centrifuging, freezing and drying to obtain a two-dimensional conductive MOF nano sheet loaded gold nano particle composite material (Au-NPs/Cu-HHTP-NSs composite material or Au-NPs/Cu-HHTP-NSs nano enzyme for short), and specifically synthesizing the composite material by the following method:
s1: measuring 500mL of the Cu-HHTP-NSs nanosheet dispersion obtained in the step 2), transferring the dispersion into a blue-mouth bottle, and stirring violently at the rotating speed of 1000 r.p.m;
s2: to the vigorously stirred dispersion obtained in step S1, 0.25mL of 1mol/L HAuCl was slowly added dropwise4After the solution is obtained, continuously stirring for 60 minutes to obtain a mixed solution A;
s3: and transferring the blue-mouthed bottle filled with the mixed solution A to a 60 ℃ oven for in-situ reduction reaction for 5 hours, cooling to room temperature, centrifuging, and freeze-drying to obtain the Au-NPs/Cu-HHTP-NSs composite material, wherein the TEM spectrogram of the Au-NPs/Cu-HHTP-NSs composite material under different amplification factors is shown in figures 1D and 1E, the gold nanoparticles in the Au-NPs/Cu-HHTP-NSs composite material are highly dispersed on the surface of the Cu-HHTP-NSs, and the average particle size of the gold nanoparticles is 3 nm.
The POD-like activities of Cu-HHTP-bulk, Cu-HHTP-NSs and Au-NPs/Cu-HHTP-NSs in example 1 of the present invention were compared by selecting TMB as a chromogenic substrate for oxidation reaction, and the specific steps were:
1) preparation of each experimental system:
experimental System TMB + H2O2+ Cu-HHTP-bulk: 30 μ L of TMB (20mM), 100 μ L H2O2(60mM)、50μL Cu-HHTP-bulk(200μg mL-1) Adding into a 5mL centrifuge tube, adding acetic acid buffer solution with pH of 3.2 to make the total volume be 3mL, and mixing well;
experimental System TMB + H2O2+ Cu-HHTP-NSs: 30 μ L of TMB (20mM), 100 μ L H2O2(60mM) and 50. mu.L of Cu-HHTP-NSs (200. mu.g mL)-1) Adding into a 5mL centrifuge tube, adding acetic acid buffer solution with pH of 3.2 to make the total volume be 3mL, and mixing well;
experimental System TMB + H2O2+ Au-NPs/Cu-HHTP-NSs 30. mu.L TMB (20mM), 100. mu. L H2O2(60mM) and 50. mu.L of Au-NPs/Cu-HHTP-NSs (200. mu.g mL)-1) Adding into a 5mL centrifuge tube, adding acetic acid buffer solution with pH of 3.2 to make the total volume be 3mL, and mixing well;
experimental System TMB + H2O2: 30 μ L of TMB (20mM) and 100 μ L H2O2(60mM) is added into a 5mL centrifuge tube, then acetic acid buffer solution with pH of 3.2 is added to make the total volume be 3mL, and the mixture is mixed evenly;
2) storing each reaction system solution for 15 minutes;
3) the obtained supernatant was tested by UV-visible spectroscopy at a wavelength in the range of 350-750nm, and the test results are shown in FIG. 3.
As can be seen from FIG. 3, the experimental system TMB + H2O2The + Au-NPs/Cu-HHTP-NSs shows obvious ultraviolet absorption peaks, which indicates that the Au-NPs/Cu-HHTP-NSs nanoenzyme has good peroxidase activity under the condition that the pH value is 3.2; experimental System TMB + H2O2The absorption peak of the + Cu-HHTP-NSs at 652nm is greatly weakened, which shows that the activity of the Cu-HHTP-NSs nanoenzyme used as a catalyst is weaker; experimental System TMB + H2O2The + Cu-HHTP-bulk has no obvious peak at 652nm, which shows that the Cu-HHTP-bulk has no catalytic activity of the peroxidase nano-enzyme basically; experimental System TMB + H2O2No peak was evident at 652nm, indicating H2O2TMB cannot be directly oxidized.
Example 2
A preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material comprises the following steps:
1) preparing ultrathin two-dimensional conductive MOF nanosheets Cu-HHTP-NSs with the thickness of 3.6nm by adopting a surfactant-assisted method and an ultrasonic stripping method;
2) ultrasonically dispersing the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs obtained in the step 1) in an ethanol solution to prepare a Cu-HHTP-NSs nanosheet dispersion liquid with the concentration of 1 g/L;
3) adding HAuCl with a certain concentration into the Cu-HHTP-NSs nanosheet dispersion liquid obtained in the step 2)4Solution of HAuCl by in-situ reduction4Reducing the gold nanoparticles into gold nanoparticles, cooling the gold nanoparticles to room temperature, centrifuging the gold nanoparticles, and carrying out freeze drying to collect the Au-NPs/Cu-HHTP-NSs composite material, wherein the Au-NPs/Cu-HHTP-NSs composite material is synthesized by the following method:
s1: weighing 500mL of Cu-HHTP-NSs nanosheet dispersion obtained in the step 2), transferring the dispersion to a blue-mouthed bottle, and violently stirring at the rotating speed of 1000 r.p.m;
s2: to the vigorously stirred dispersion obtained in step S1, 0.5mL of 1mol/L HAuCl was slowly added dropwise4After the solution is stirred for 60 minutes, a mixed solution A is obtained,
s3: and transferring the blue-mouth bottle filled with the mixed solution A to a 60 ℃ oven for in-situ reduction reaction for 5 hours, cooling to room temperature, centrifuging, and freeze-drying to obtain the Au-NPs/Cu-HHTP-NSs composite material, wherein the average particle size of the gold nanoparticles is 5 nm. .
Example 3
A preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material comprises the following steps:
1) preparing ultrathin two-dimensional conductive MOF nanosheets Cu-HHTP-NSs with the thickness of 3.6nm by adopting a surfactant-assisted method and an ultrasonic stripping method;
2) ultrasonically dispersing the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs obtained in the step 1) in an ethanol solution to prepare a Cu-HHTP-NSs nanosheet dispersion liquid with the concentration of 1 g/L;
3) adding HAuCl with a certain concentration into the Cu-HHTP-NSs nanosheet dispersion liquid obtained in the step 2)4Solution of HAuCl by in-situ reduction4Reducing to gold nano-particles, cooling to room temperature, centrifuging, and freeze-dryingThe Au-NPs/Cu-HHTP-NSs composite material is collected in a drying way, and is synthesized by the following method:
s1: weighing 500mL of Cu-HHTP-NSs nanosheet dispersion obtained in the step 2), transferring the dispersion to a blue-mouthed bottle, and violently stirring at the rotating speed of 1000 r.p.m;
s2: to the vigorously stirred dispersion obtained in step S1, 1mL of 1mol/L HAuCl was slowly added dropwise4After the solution is stirred for 60 minutes, a mixed solution A is obtained,
s3: and transferring the blue-mouth bottle filled with the mixed solution A to a 60 ℃ oven for in-situ reduction reaction for 5 hours, cooling to room temperature, centrifuging, and freeze-drying to obtain the Au-NPs/Cu-HHTP-NSs composite material, wherein the average particle size of the gold nanoparticles is 10 nm.
Example 4
The Au-NPs/Cu-HHTP-NSs composite material prepared in the embodiment 2 is used for preparing a hydrogen peroxide electrochemical sensor (a double nano enzyme-based electrochemical sensor), and the double nano enzyme-based electrochemical sensor is prepared by the following method:
1) transferring the Au-NPs/Cu-HHTP-NSs composite material to a glassy carbon electrode GCE to form an Au-NPs/Cu-HHTP-NSs/GCE modified electrode;
2) the Au-NPs/Cu-HHTP-NSs/GCE modified electrode is used as a working electrode and inserted into an electrolytic cell, Ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, 0.1M (pH 7.4) phosphate buffer solution PBS is used as electrolyte, a chronoamperometry-current response curve of different hydrogen peroxide concentrations is measured by adopting a chronoamperometry method, a linear relation between the hydrogen peroxide concentrations and corresponding currents is fitted, and a ratiometric electrochemical sensor based on the sensing interface of the Au-NPs/Cu-HHTP-NSs/GCE modified electrode, namely a double-nano enzyme-based electrochemical sensor, is constructed.
Specifically, with cyclic voltammetry, a potential was set in the range of-1 to 0.6V, and as shown in fig. 4, the hydrogen peroxide concentration was increased, and the peak current intensity thereof was increased as the hydrogen peroxide concentration was increased. The amperometric response of the sensor is further researched by adopting a chronoamperometry method, and as shown in an i-t curve, as shown in fig. 5 and 6, the current gradually increases along with the increase of the concentration of the hydrogen peroxide, the current shows a step-up trend, and the current can be increasedTo reach a steady state value within 3 s. From the results, the application of the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs loaded ultra-small gold nanoparticle modified glassy carbon electrode Au-NPs/Cu-HHTP-NSs/GCE to the hydrogen peroxide electrochemical sensor is good in electrochemical sensing performance, high in sensitivity and low in detection limit, wherein the detection limit is as low as 5.6 nanomoles/liter, and the sensitivity is 188.1 muA cm-2mM-1。
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A preparation method of a two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material is characterized by comprising the following steps:
1) preparing ultrathin two-dimensional conductive MOF nanosheets Cu-HHTP-NSs by adopting a surfactant-assisted method and an ultrasonic stripping method;
2) ultrasonically dispersing the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs obtained in the step 1) in an ethanol solution to prepare a Cu-HHTP-NSs nanosheet dispersion liquid with a certain concentration;
3) adding HAuCl with a certain concentration into the Cu-HHTP-NSs nanosheet dispersion liquid obtained in the step 2)4Solution of HAuCl by in-situ reduction4Reducing the metal nano particles into gold nano particles, cooling to room temperature, centrifuging, and freeze-drying to obtain the two-dimensional conductive MOF nano sheet loaded gold nano particle composite material.
2. The preparation method of the two-dimensional conductive MOF nanosheet-supported gold nanoparticle composite material of claim 1, wherein the thickness of the ultrathin two-dimensional conductive MOF nanosheet Cu-HHTP-NSs in step 1) is 2-10 nm.
3. The preparation method of the two-dimensional conductive MOF nanosheet-supported gold nanoparticle composite material of claim 1, wherein the concentration of the Cu-HHTP-NSs nanosheet dispersion in step 2) is 0.1-1 g/L.
4. The preparation method of the two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material of claim 1, wherein the two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material in step 3) is synthesized by:
s1: measuring 500-1000mL of Cu-HHTP-NSs nanosheet dispersion obtained in the step 2), and violently stirring at the rotating speed of 800-1000 r.p.m;
s2: slowly dropwise adding 0.25mL-1mL of 1mol/L HAuCl into the dispersion liquid of the step S14After the solution is dissolved, continuously stirring for 20-60min to obtain a mixed solution A;
s3: and (4) placing the mixed solution A obtained in the step S2 at 40-60 ℃ for in-situ reduction reaction, cooling to room temperature after reacting for 3-5 hours, centrifuging, and freeze-drying to obtain the two-dimensional conductive MOF nanosheet-loaded gold nanoparticle composite material.
5. The preparation method of the two-dimensional conductive MOF nanosheet-supported gold nanoparticle composite material of claim 1, wherein the average particle size of gold nanoparticles in the two-dimensional conductive MOF nanosheet-supported gold nanoparticle composite material of step 3) is 2-10 nm.
6. A preparation method of a double nano enzyme-based electrochemical sensor is characterized by comprising the following steps:
1) transferring the two-dimensional conductive MOF nanosheet supported gold nanoparticle composite of any one of claims 1 to 5 onto a Glassy Carbon Electrode (GCE) to form an Au-NPs/Cu-HHTP-NSs/GCE modified electrode;
2) inserting the Au-NPs/Cu-HHTP-NSs/GCE modified electrode serving as a working electrode into an electrolytic cell, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, taking 0.1M phosphoric acid buffer solution PBS as electrolyte, measuring an amperometric timing-current response curve of different hydrogen peroxide concentrations by adopting a timing current method, fitting a linear relation between the hydrogen peroxide concentration and corresponding current, and constructing a ratiometric electrochemical sensor based on the sensing interface of the Au-NPs/Cu-HHTP-NSs/GCE modified electrode, namely a double-nanoenzyme-based electrochemical sensor.
7. The use of the double nanoenzyme-based electrochemical sensor prepared according to claim 6 for the sensitive detection of hydrogen peroxide in cancer cells.
CN202210175222.1A 2022-02-25 2022-02-25 Preparation method and application of two-dimensional conductive MOF nanosheet loaded gold nanoparticle composite material Pending CN114632547A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115716995A (en) * 2022-11-24 2023-02-28 华东师范大学 Preparation method of metal organic framework-gold composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111155143A (en) * 2020-01-07 2020-05-15 中国科学院化学研究所 Preparation method of two-dimensional layered metal organic framework nano material
CN113235118A (en) * 2021-05-17 2021-08-10 苏州大学 Electrochemical synthesis method of conductive metal organic framework anode
CN113671005A (en) * 2021-07-01 2021-11-19 广州大学 Copper ion selective electrode based on MOF, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111155143A (en) * 2020-01-07 2020-05-15 中国科学院化学研究所 Preparation method of two-dimensional layered metal organic framework nano material
CN113235118A (en) * 2021-05-17 2021-08-10 苏州大学 Electrochemical synthesis method of conductive metal organic framework anode
CN113671005A (en) * 2021-07-01 2021-11-19 广州大学 Copper ion selective electrode based on MOF, and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WENJIAO DANG等: "AuNPs-NH2/Cu-MOF modified glassy carbon electrode as enzyme-free electrochemical sensor detecting H2O2", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, pages 1 - 7 *
ZHIYONG WANG 等: "Ultrathin two-dimensional conjugated metal–organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis", CHEMICAL SCIENCE, vol. 11, no. 29, pages 7665 - 7671 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115716995A (en) * 2022-11-24 2023-02-28 华东师范大学 Preparation method of metal organic framework-gold composite material

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