CN113155915B - Titanium mesh supported cobalt-based metal organic framework graphene nanosheet array and application thereof - Google Patents
Titanium mesh supported cobalt-based metal organic framework graphene nanosheet array and application thereof Download PDFInfo
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Abstract
The invention provides a titanium mesh supported cobalt-based metal organic framework graphene nanosheet array and application thereof, wherein the preparation process of the graphene nanosheet array comprises the following steps: the preparation process comprises the following steps: preparing Co-GR/MOF by adopting a one-step hot melting method, and then preparing Co-GR/MOF/TM; the application is in particular to NO 2 Detecting the concentration, namely arraying the graphene nanosheets in NO 2 When applied to gas detection, the method is found to be applied to NO 2 The sensor has excellent sensing performance, good sensitivity and stability and low detection limit.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a titanium mesh supported cobalt-based metal organic framework graphene nanosheet array and application thereof.
Background
In recent years, the rapid development of industry brings great convenience to our lives and also brings about a great deal of environmental pollution problems. Among them, nitrogen dioxide, as a common harmful gas, is one of the important precursors that cause acid rain, photochemical smog and air pollutants PM2.5, and seriously threatens human health. Therefore, it is necessary to develop a high-performance sensor for in-situ detection of trace nitrogen dioxide.
At present, researches on the application of graphene in specific detection of nitrogen dioxide gas are widely reported, but the defects of low sensitivity, poor room-temperature desorption performance and the like exist at present, so that the sensitivity of a sensor is poor in the process of repeated use, and the detection result has no repeatability. The Metal Organic Framework (MOF) is formed by combining metal ions and organic ligands through self-assembly, and has high porosity and large specific surface area. However, the traditional MOF has the problems of disordered orientation, low conductivity and the like, and the application of the traditional MOF in the field of electrochemical sensing is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a graphene nanosheet array with a titanium net supported cobalt-based metal organic framework and application thereof, the graphene nanosheet array can effectively solve the problem of graphene agglomeration by using a one-step solvothermal method to prepare Co-GR/MOF, the adsorption sites on the surface of graphene are fully exposed, and meanwhile, the constructed three-dimensional framework structure can greatly increase the penetrability of target molecules and increase the contact area between a sensing layer and the target molecules, so that the comprehensive performance of the Co-GR/MOF/TM sensor can be improved; arraying the graphene nanosheets in NO 2 The gas detection aspect is applied to the discovery of NO 2 Has excellent sensing performance, good sensitivity, stability and low detection limit, and can measure 20ppb NO in a laboratory 2 The gas has better sensing performance.
The technical scheme of the invention is as follows:
a titanium mesh supported cobalt-based metal organic framework graphene nanosheet array (Co-GR/MOF/TM) is prepared by the following steps: preparing Co-GR/MOF by adopting a one-step hot melting method, and then preparing Co-GR/MOF/TM;
wherein, in the one-step hot melt method, graphene is added to N, N-dimethylformamide, and then CoCl is added thereto 2 ·6H 2 And mixing the O and the terephthalic acid uniformly, and then continuously adding ethanol and ultrapure water.
The titanium mesh supported cobalt-based metal organic framework graphene nanosheet array (Co-GR/MOF/TM) is prepared by the following steps:
(1) One-step solvothermal processPreparation of Co-GR/MOF: adding 0.02-0.04 mol of Graphene (GR) into 30-100 mL of N, N-Dimethylformamide (DMF), performing ultrasonic treatment for 10-20 min, and then adding CoCl 2 ·6H 2 Stirring O and terephthalic acid (TPA) for 10-30min to obtain a uniformly mixed solution; then, slowly adding 2.5-7.5 mL of ethanol and 2.5-7.5 mL of ultrapure water into the mixed solution, and continuously stirring for 30min to obtain a solution I;
(2) Preparation of Co-GR/MOF/TM: transferring the solution I into a stainless steel autoclave lined with teflon, putting a titanium mesh into the autoclave, and keeping the temperature at 125-150 ℃ for 12-18 h; and after cooling, taking out the product, washing the product with ultrapure water, and drying the product for 4 to 6 hours at the temperature of between 60 and 80 ℃ to obtain Co-GR/MOF/TM.
The graphene has excellent conductivity and large specific surface area, and the graphene is added into the solution I, so that the electron transfer rate of the obtained Co-GR/MOF/TM in the sensing process is improved, the sensitivity of a target product is increased, and the electrochemical performance of the Co-GR/MOF/TM is improved. The stability of Co-GR/MOF/TM was improved by using titanium mesh with solution I in the presence of cobalt.
The sensing layer is of a three-dimensional network structure, so that target molecules can enter the inside of the sensing layer, and compared with a two-dimensional structure, the target molecules can contact with adsorption sites inside the sensing layer through the outer surface of the sensing layer, so that the penetrability of the target molecules can be improved.
Preferably, in the step (1), the graphene is nano graphene, and the particle size is as follows: 20-100nm.
Preferably, in the step (1), the addition amount of the graphene is 0.03mol, the addition amount of N, N-Dimethylformamide (DMF) is 80mL, the addition amount of ethanol is 5mL, and the addition amount of ultrapure water is 7mL.
Preferably, in step (1), coCl 2 ·6H 2 The addition amount of O is as follows: 0.001 to 0.003mol; the addition amount of terephthalic acid is as follows: 0.001 to 0.003mol.
The cobalt-based metal organic framework titanium mesh supports graphene nanosheet array (Co-GR/MOF/TM) in NO 2 Application of gas detection to NO 2 Has excellent sensing performance, good sensitivity and stability and excellent detectionLimit, laboratory determination of 20ppb of NO 2 The gas has better sensing performance, and the value is far lower than NO proposed by the national environmental air quality standard 2 Detection limit value (53 ppb) and has practicability.
Preferably, the above-mentioned application is in particular as a sensor for NO 2 The application of gas detection.
Preferably, the Co-GR/MOF/TM sensor is NO 2 The detection method comprises the following steps:
(1) Placing a Co-GR/MOF/TM sensor in a gas testing bottle, connecting two ends of the sensor with an electrochemical workstation, and testing in a constant voltage mode;
(2) Test NO in bottle 2 Is regulated by means of a gas flow meter (NO) 2 /N 2 ) Mixer and pure N 2 Flow rate control of (2);
(3) Before testing, the sensors were at pure N 2 Stabilizing the atmosphere for a period of time to remove interfering gases from the test vial, and recording the baseline conductivity as G after the baseline current has substantially stabilized 0 (ii) a When in test, NO with a certain concentration is introduced into a test bottle 2 Gas, recording the current signal at this time as G g (this is the adsorption process), followed by NO 2 The gas is closed and pure N2 is introduced to flush the test bottle, and the current is reduced to the initial level (the desorption process); the process of response recovery is completed after the above circulation;
(4) The performance of the sensor was evaluated according to a conductivity change rate (response value) calculation formula, which is as follows:
preferably, to avoid interference of the gas flow rate with the sensing properties, the total flow rate of gas in the test bottle is maintained at 1000sccm throughout the test.
Compared with the prior art, the invention has the beneficial effects that:
1. the Co-GR/MOF is prepared by adopting a one-step method, the difficult problem of agglomeration and the structural problem of the nano material are effectively solved, in addition, the graphene nanosheet layer formed by adding the nano graphene material improves the rapid electron transfer capability and the sensitive reaction to the target, and shows good electrochemical sensing performance.
2. Under the support of a Titanium Mesh (TM), the Co-GR/MOF is covered on the surface of the TM in a nano-sheet structure, so that the conductivity and catalytic activity of the titanium mesh to surface electronic defects are improved, the Co-GR/MOF/TM sensor has a uniform cavity and a high specific surface area, a target area enrichment effect is displayed, the anti-interference performance is improved, and the accuracy of a detection result is further improved.
3. Use of Co-GR/MOF/TM sensor for NO 2 The detection has the advantages of high sensing sensitivity, good stability and low detection limit, and the NO can be accurately and accurately detected by using the sensor 2 And (6) detecting.
Drawings
In order to more clearly illustrate the embodiments or prior art solutions of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows a Co-GR/MOF/TM and TM sensor pair of 500ppb NO 2 The response curve of (c).
FIG. 2 shows Co-GR/MOF/TM sensor for different concentrations of NO 2 The response curve of (c).
FIG. 3 is a graph of the response of a Co-GR/MOF/TM sensor to different gases.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
Example 1:
a cobalt-based metal organic framework titanium mesh supported graphene nanosheet array (Co-GR/MOF/TM) is prepared by the following steps:
(1) Preparing Co-GR/MOF by a one-step solvothermal method: 0.03mol of Graphene (GR) was added to 80mL of N, N-Dimethylformamide (DMF), sonicated for 15min, and 0.002mol of CoCl 2 ·6H 2 Adding O and 0.0022mol of terephthalic acid (TPA) into the solution, and stirring for 20min to obtain a uniformly mixed solution; then, slowly adding 5mL of ethanol and 7mL of ultrapure water into the mixed solution, and continuously stirring for 30min to obtain a solution I;
(2) Preparation of Co-GR/MOF/TM: transferring the solution I into a stainless steel autoclave lined with Teflon, putting a titanium net, and keeping the solution at 140 ℃ for 14 hours; after cooling, the product was taken out, washed with ultrapure water, and dried at 70 ℃ for 5h to obtain Co-GR/MOF/TM.
Example 2:
a cobalt-based metal organic framework titanium mesh supported graphene nanosheet array (Co-GR/MOF/TM) is prepared by the following steps:
(1) Preparing Co-GR/MOF by a one-step solvothermal method: 0.02mol of Graphene (GR) was added to 30mL of N, N-Dimethylformamide (DMF), sonicated for 10min, and then 0.001mol of CoCl was added thereto 2 ·6H 2 Stirring O and 0.001mol of terephthalic acid (TPA) for 10min to obtain a uniformly mixed solution; then, slowly adding 2.5mL of ethanol and 2.5mL of ultrapure water into the mixed solution, and continuously stirring for 30min to obtain a solution I;
(2) Preparation of Co-GR/MOF/TM: transferring the solution I into a stainless steel autoclave lined with Teflon, putting a titanium net, and keeping at 125 ℃ for 12 hours; after cooling, taking out the product, washing with ultrapure water, and drying at 60 ℃ for 4h to obtain Co-GR/MOF/TM.
Example 3:
a cobalt-based metal organic framework titanium mesh supported graphene nanosheet array (Co-GR/MOF/TM) is prepared by the following steps:
(1) Preparing Co-GR/MOF by a one-step solvothermal method: 0.04mol of Graphene (GR) was added to 100mL of N, N-Dimethylformamide (DMF), sonicated for 20min, and then added thereto0.003mol of CoCl are added 2 ·6H 2 O and 0.003mol of terephthalic acid (TPA) are stirred for 30min to obtain a uniformly mixed solution; then, slowly adding 7.5mL of ethanol and 7.5mL of ultrapure water into the mixed solution, and continuously stirring for 30min to obtain a solution I;
(2) Preparation of Co-GR/MOF/TM: transferring the solution I into a stainless steel autoclave lined with teflon, putting a titanium mesh into the autoclave, and keeping the temperature at 150 ℃ for 18 hours; after cooling, the product is taken out, washed by ultrapure water and dried for 6h at 80 ℃ to obtain Co-GR/MOF/TM.
Experimental example 1: sensor pair NO 2 Determination of detectability and reproducibility
Placing the Co-GR/MOF/TM obtained in the example 1 in a gas testing bottle as a sensor (namely a working electrode), connecting two ends of the electrode with an electrochemical workstation of which the model is CHI 660E, testing a current-time curve by adopting a constant voltage mode at room temperature, wherein the voltage is 1V, the sampling interval is 0.1s, and the total flow rate of gas in the testing bottle is always kept to be 1000sccm during testing;
as can be seen from FIG. 1, when NO is introduced 2 The conductivity of the sensor increases rapidly until NO 2 Off, the conductivity dropped rapidly, up to the initial level, indicating that the Co-GR/MOF/TM sensor of example 1 has the ability to detect NO 2 The ability of the cell to perform. The standard deviation of different cycles of the Co-GR/MOF/TM sensor is found to be less than 10 percent by repeating the cycle for multiple times, which shows that the sensor has good repeatability.
Experimental example 2: sensor pair NO 2 Determination of detection Limit
Co-GR/MOF/TM from example 1 was used as a sensor and mounted in an electrochemical workstation of model CHI 660E, and the test was carried out at room temperature in a constant voltage mode (voltage 1V) with stepwise introduction of NO at different concentrations into the test bottles 2 Gas with concentrations of 20ppb, 40ppb, 100ppb, 200ppb, 400ppb, 600ppb, 800ppb, 1ppm, 1.2ppm, 1.5ppm, respectively, wherein N is still used in desorption 2 And (4) washing the test bottle, and keeping the total flow rate of the gas in the test bottle at 1000sccm all the time in the test process.
The results are shown in FIG. 2, and it can be seen that with NO 2 Gradual increase of concentrationThe sensing ability of the Co-GR/MOF/TM sensor is enhanced, and the response value is changed along with NO 2 Increase in concentration;
wherein the Co-GR/MOF/TM sensor is coupled to NO 2 Shows obvious change in response value, and can be seen in combination with FIG. 2, the Co-GR/MOF/TM provided in example 1 is used as a sensor for NO 2 When the detection Limit (LOD) is 20ppb, the sensor has a complete adsorption/desorption curve for NO2 gas, and the Co-GR/MOF/TM sensor has the advantages of low detection limit and high sensitivity; the detection limit is far lower than NO provided by the national environmental air quality standard 2 The detection limit value (53 ppb), therefore, the proposed Co-GR/MOF/TM sensor has excellent electrochemical detection capability.
Experimental example 3: sensor pair NO 2 Determination of gas and other interfering gas sensing properties
The Co-GR/MOF/TM sensor of example 1 was mounted in an electrochemical workstation of model CHI 660E and tested in constant voltage mode (voltage 1V) at room temperature, into which 500ppb NO was sequentially introduced 2 、500ppb NO、500ppb NH 3 、2000ppm O 2 、2000ppm H 2 O、2000ppm CO 2 The total flow rate of the gas in the test bottle is kept to be 1000sccm all the time during the test.
As can be seen in FIG. 3, the Co-GR/MOF/TM sensor is only sensitive to NO 2 The gas has obvious response, and when other gases are introduced, the conductivity has no obvious change, which shows that the sensor has good anti-interference performance, and can effectively avoid the interference of common substances in the actual use process.
Although the present invention has been described in detail by referring to the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A preparation method of a titanium mesh supported cobalt-based metal organic framework graphene nanosheet array is characterized by comprising the following steps:
(1) Preparing Co-GR/MOF by a one-step solvothermal method: adding 0.02-0.04 mol of graphene into 30-100 mL of N, N-dimethylformamide, performing ultrasonic treatment for 10-20 min, and then adding CoCl 2 ·6H 2 Stirring O and terephthalic acid for 10-30min to obtain a uniformly mixed solution; then, slowly adding 2.5-7.5 mL of ethanol and 2.5-7.5 mL of ultrapure water into the mixed solution, and continuously stirring for 30min to obtain a solution I;
(2) Preparation of Co-GR/MOF/TM: transferring the solution I into a stainless steel autoclave lined with teflon, putting a titanium mesh into the autoclave, and keeping the temperature at 125-150 ℃ for 12-18 h; after cooling, taking out the product, washing the product with ultrapure water, and drying the product for 4 to 6 hours at the temperature of between 60 and 80 ℃ to obtain Co-GR/MOF/TM;
the titanium mesh supported cobalt-based metal organic framework graphene nanosheet array is in NO 2 The gas sensor is applied to the aspect of gas detection, in particular to NO as a sensor 2 The application of gas detection.
2. The preparation method of the titanium mesh-supported cobalt-based metal organic framework graphene nanosheet array as defined in claim 1, wherein in step (1), the graphene is nanographene with a particle size of: 20-100nm.
3. The preparation method of a titanium mesh-supported cobalt-based metal organic framework graphene nanosheet array as claimed in claim 1, wherein in step (1), the amount of graphene added is 0.03mol, the amount of n, n-dimethylformamide added is 80mL, the amount of ethanol added is 5mL, and the amount of ultrapure water added is 7mL.
4. The preparation method of the titanium mesh-supported cobalt-based metal organic framework graphene nanosheet array as claimed in claim 1, wherein the preparation method is characterized in thatCharacterized in that, in step (1), coCl 2 ·6H 2 The addition amount of O is as follows: 0.001-0.003 mol; the addition amount of terephthalic acid is as follows: 0.001 to 0.003mol.
5. The preparation method of the titanium mesh-supported cobalt-based metal organic framework graphene nanosheet array as claimed in claim 1, wherein Co-GR/MOF/TM is used as a sensor in NO 2 The detection method comprises the following steps:
(1) Placing a Co-GR/MOF/TM sensor in a gas testing bottle, connecting two ends of the sensor with an electrochemical workstation, and testing in a constant voltage mode;
(2) Test of NO in bottle 2 Concentration of (3) adjusting the mixer and pure N using a gas flow meter 2 Flow rate control of (2);
(3) Before testing, the sensors were at pure N 2 The atmosphere is stabilized for a period of time to remove interfering gases from the test bottle and when the baseline current is substantially stabilized, the baseline conductivity is recorded as G 0 (ii) a When in test, NO with certain concentration is introduced into the test bottle 2 Gas, recording the current signal at this time as G g Followed by NO 2 Closing the gas, introducing pure N2 to flush the test bottle, and waiting for the current to be reduced to an initial level; the process of response recovery is completed after the above circulation;
(4) Evaluating the performance of the sensor according to a conductivity change rate calculation formula, wherein the formula is as follows:
6. the preparation method of the titanium mesh-supported cobalt-based metal organic framework graphene nanosheet array as defined in claim 5, wherein a total flow rate of gas in the test bottle is maintained at 1000sccm throughout the testing process.
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