CN113624821B - Containing MN2O2Carbon material of unit, preparation method and application for detecting NO - Google Patents
Containing MN2O2Carbon material of unit, preparation method and application for detecting NO Download PDFInfo
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- CN113624821B CN113624821B CN202110920581.0A CN202110920581A CN113624821B CN 113624821 B CN113624821 B CN 113624821B CN 202110920581 A CN202110920581 A CN 202110920581A CN 113624821 B CN113624821 B CN 113624821B
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- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
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Abstract
The invention belongs to the field of gas-sensitive material synthesis technology and electrochemical detection, and particularly relates to a gas-sensitive material containing MN2O2A carbon material of a unit, a preparation method and application for detecting nitric oxide. The MN2O2The structure of the unit is shown as formula I:
in formula I, M = Sc, ti, V, cr, mn, fe, co, ni, cu, zn or Bi; r is1＝‑CH2‑CH2-, -Ph-or-Ch-. The invention adopts a system containing MN2O2Detection of nitric oxide by carbon material of unit, MN with special structure2O2The unit can provide excellent nitric oxide catalytic activity, so that the MN is contained2O2The carbon material of the unit is applied to the actual detection process of nitric oxide, has low detection limit and can realize sensitive detection. Meanwhile, the material is a heterogeneous material, is insoluble in water when detecting nitric oxide in an aqueous solution, can be recycled, and greatly reduces the detection cost.
Description
Technical Field
The invention belongs to the field of gas-sensitive material synthesis technology and electrochemical detection, and particularly relates to a gas-sensitive material containing MN2O2A carbon material of a unit, a preparation method and application for detecting nitric oxide.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Nitric oxide, a newly recognized information molecule and "star molecule", has attracted considerable attention from life sciences and related disciplines due to its important physiological role in the living body and one of the important factors that destroy the ozone layer. Recently, it has been reported that nitric oxide plays an important regulatory role in plant growth and development and defense against viruses. Major problems currently faced with respect to the detection of pure nitric oxide gas include:
(1) Nitric oxide is chemically very reactive and has a short half-life due to its unpaired free radical electron. The detection process needs to be free from oxygen, which requires that the detection process needs to be completed in an extremely short time.
(2) Due to the instability of nitric oxide molecules, the lower limit of dilution is 5ppb when preparing low concentrations of nitric oxide, which is detrimental for the investigation of nitric oxide sensor materials.
There are many conventional methods for measuring nitric oxide, and the methods include spectrophotometry, electron spin spectrometry, chemiluminescence, electrochemistry, bioassay, electromagnetic resonance spectrometry, chemiluminescence, and laser-induced fluorescence. The electrochemical method has the characteristics of real-time, continuous and on-site measurement and is widely popularized and applied, so that the development of the high-efficiency gas sensor material based on the electrochemical means and capable of being directly used for detecting nitric oxide is of great significance.
At present, a metal-salen cross-linked material is widely used for detecting nitric oxide by an electrochemical method, for example, a Co-salen/Nafion modified electrode is disclosed in the prior art, nitric oxide can be subjected to electrocatalytic oxidation on the Co-salen/Nafion membrane modified electrode, and then nitric oxide in natural seawater can be measured, but the metal-salen material is a homogeneous material and is difficult to recover after being applied in an aqueous solution, and the catalytic activity of the metal-salen material is limited, so that sensitive detection is difficult to perform when the amount of nitric oxide is low. In addition, the metal-salen material has low conductivity, and is low in efficiency when used for detecting nitric oxide by an electrochemical method.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a Mobile Node (MN)2O2The invention relates to a carbon material of a unit, a preparation method thereof and application thereof in detecting nitric oxide, and the invention adopts a material containing MN2O2Detection of nitric oxide by carbon material of unit, MN with special structure2O2The unit can provide excellent nitric oxide catalytic activity, further has a lower detection limit, and can realize sensitive detection. Furthermore, the introduction of the carbon material can provide good conductivity and improve detection efficiency. Meanwhile, the material is a heterogeneous material, is insoluble in water when detecting nitric oxide in an aqueous solution, can be recycled, and greatly reduces the detection cost.
To achieve the above object, the present invention provides, in a first aspect, a MN-containing network2O2Carbon material of unit, MN2O2The structure of the unit is shown as formula I:
in formula I, M = Sc, ti, V, cr, mn, fe, co, ni, cu, zn or Bi; r is1＝-CH2-CH2-, -Ph- (-Ph-is phenyl) or-Ch- (-Ch-is cyclohexane).
The second aspect of the present invention provides a method for making the above MN2O2A method of making a carbon material of a unit, comprising the steps of:
ball-milling a precursor M-Salen and a carbon material according to a certain proportion and calcining at high temperature to prepare the Mn-containing material2O2A unit carbon material.
The third aspect of the present invention provides an MN2O2Use of a carbon material of a cell for detecting nitric oxide.
One or more embodiments of the present invention have at least the following advantageous effects:
(1) The invention adopts a system containing MN2O2Detection of nitric oxide by carbon material of unit, MN with special structure2O2The unit can provide excellent nitric oxide catalytic activity, so that the MN is contained2O2The carbon material of the unit is applied to the process of detecting the actual content of nitric oxide, has low detection limit, and particularly can achieve the lowest detection concentration of 8ppb in the process of detecting the exhaled breath of a human body, thereby realizing high-sensitivity detection.
(2) The invention provides MN2O2The carbon material of unit is heterogeneous material, when detecting nitric oxide, is difficult for dissolving in the aquatic, can retrieve after detecting so, realizes recycling, greatly reduced the detection cost, also avoided the pollution to the water simultaneously.
(3) The invention converts MN into MN2O2The units are supported in a carbon material, the carbon can be MN2O2The cell provides excellent conductivity such that MN is contained2O2When the carbon material of the unit is applied to the detection of nitric oxide by an electrochemical method, the detection effect is better.
(4) The MN is contained2O2The synthesis conditions for the carbon unit material were easy to handle, and the carbon material used for the support was inexpensive and readily available, so that MN was contained in example 12O2The carbon material of the unit can be synthesized in large quantities.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a drawing of a MN with a view to illustrating the present invention2O2A schematic flow chart of the preparation of the unit carbon material;
FIG. 2 shows the NiN content in example 12O2High resolution electron microscopy images of the unit carbon material;
FIG. 3 shows the NiN content in example 12O2A spherical aberration electron micrograph of the unit carbon material;
FIG. 4 shows the NiN content in example 12O2Elemental profile of a unit carbon material;
FIG. 5 shows the NiN content in example 12O2Detecting a cyclic voltammetry curve of solution phase nitric oxide by using a unit carbon material;
FIG. 6 shows the NiN content in example 12O2Detecting a comparison graph of the concentration of nitric oxide in the exhaled gas of the human body and peak current by using the unit carbon material;
FIG. 7 shows the precursors Ni-Salen and NiN-containing in example 12O2A peak current contrast graph of detecting 8ppb of human exhaled gas nitric oxide by using a unit carbon material;
FIG. 8 shows the NiN content in example 12O2Time versus peak current plot of 1.8nM nitric oxide in the single carbon material detection solution phase.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the Co-salen material widely used in the prior art for detecting nitric oxide is a homogeneous material, and is difficult to recover after being applied in an aqueous solution, and the Co-salen material has a limited catalytic activity, so that it is difficult to perform a sensitive detection when the amount of nitric oxide is low. In addition, the metal-salen material has low conductivity, and is low in efficiency when used for detecting nitric oxide by an electrochemical method.
In order to solve the above technical problems, a first aspect of the present invention provides a MN-containing network2O2Carbon material of unit, MN2O2The structure of the unit is shown as formula I:
in formula I, M = Sc, ti, V, cr, mn, fe, co, ni, cu, zn or Bi; r is1＝-CH2-CH2-, -Ph- (-Ph-is phenyl) or-Ch- (-Ch-is cyclohexyl).
The invention provides MN2O2The carbon material of the unit is prepared by mixing and sintering an M-Salen complex and the carbon material, compared with the M-Salen complex, MN2O2The unit generates structural change, and MN is destroyed in the calcining process2O2The benzene ring structures at the two ends are reserved for the MN2O2And (5) structure. Therefore, this particular MN2O2Compared with an M-Salen complex, the structure of the complex improves the activity of catalyzing nitric oxide, so that the MN is provided by the invention2O2The carbon material of the unit has lower detection lower limit in the process of applying to the detection of nitric oxide, realizes more sensitive detection, and particularly has the lowest detection lower limit of 8ppb when being applied to the detection of nitric oxide in human exhaled breath.
Moreover, the M-Salen complex is a homogeneous material, although the M-Salen complex can detect nitric oxide in a solution phase by utilizing the catalytic activity of the M-Salen complex, the M-Salen complex has certain water solubility and poor recycling property, so that the detection cost is higher, and meanwhile, when the M-Salen complex is used for detecting nitric oxide in a natural water body, the recovery is difficult, so that certain water body pollution is caused. The MN contained in the invention2O2The carbon material of the unit is a heterogeneous material, and is insoluble in water when detecting nitric oxide in an aqueous solution, so that the carbon material can be recycled after the detection is finished in sequence, the repeated utilization is realized, the detection cost can be effectively reduced, and the pollution to a water body is also avoided.
In addition, the present invention associates MN with2O2The unit is supported in a carbon material, the carrier carbon material can be MN2O2The unit provides excellent conductivity, so that the unit has more efficient detection effect when being applied to the detection of nitric oxide in human exhaled breath in an electrochemical method.
The second aspect of the present invention provides an MN2O2A method of making a carbon material of a unit, comprising the steps of:
ball-milling a precursor M-Salen and a carbon material according to a certain proportion and calcining at high temperature to prepare the Mn-containing material2O2A unit carbon material.
Wherein, during the calcination process, the structure of the precursor M-Salen is changed to form MN2O2The units, while attached in a carbon support, form a composite.
The carbon material in the invention is a carbon material, has no special requirement, and specifically comprises a commercial carbon material and a carbon material prepared by a conventional experimental technology, and is preferably one or more of acetylene black, carbon black, graphene and carbon nanotubes.
The preparation process contains MN2O2The addition ratio of the precursor of the unit to the carbon material has an important influence, the high proportion of the carbon material can reduce the proportion of catalytic active ingredients, and is not favorable for high-efficiency nitric oxide detection, and the low proportion of the carbon material can cause that the precursor M-Salen can not be fully converted into MN2O2The unit, too, cannot perform highly sensitive detection. Therefore, as a preferred embodiment, the mass ratio of the precursor M-Salen to the carbon material is 1: 1:1.
Further, the calcination temperature is 200 to 900 ℃, preferably 300 to 900 ℃, and the calcination time is 1 to 12 hours, preferably 2 to 3 hours.
Further, containing MN2O2The preparation method of the unit carbon material specifically comprises the following steps:
mixing and ball-milling a precursor M-Salen and a carbon material according to the mass ratio of 1-100, putting the mixture into a tube furnace, introducing inert gas into the mixture, and calcining the mixture at 200-900 ℃ for 1-12 hours to obtain the Mn-containing material2O2A unit carbon material.
The precursor M-Salen is a material which can be directly obtained in the prior art;
as a preferred embodiment, the precursorThe preparation method of the M-Salen comprises the following steps: taking salicylaldehyde, metal salt and amine compound as organic ligands and absolute ethyl alcohol as a reaction solvent to react to prepare the MN2O2A precursor M-Salen of a carbon material;
further, the metal salt compound is acetate, chloride, perchlorate, sulfate, nitrate or diethyl salt.
Further, the amine compound is ethylenediamine, cyclohexanediamine or phenylenediamine.
The third aspect of the present invention provides an MN2O2Use of carbon materials of units for the detection of nitric oxide, including but not limited to:
(1) Detecting nitric oxide in exhaled breath of a human body;
(2) And detecting nitric oxide in the solution phase.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
1) Containing NiN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 1 g of precursor M-Salen and 1 g of commercial acetylene black for 15 minutes by using a ball mill, calcining for 2 hours in a 300 ℃ tubular furnace with nitrogen flow, after the tubular furnace is cooled to room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the NiN-containing material2O2The yield of the unit carbon material is 56-80%.
FIG. 2 shows the NiN content obtained in this example2O2The high-resolution electron microscope image of the unit carbon material shows that the material presents a cloud-like appearance, and the spherical aberration electron microscope image of the material is shown in FIG. 3, so that nickel atoms dispersed in a single atomic form can be clearly seen; FIG. 4 is a diagram of the distribution of elements of the material, illustrating the uniform distribution of elements Ni, N, O, C, etc. in the carbon material.
Example 2
1) Containing CuN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 1 g of precursor Cu-Salen and 1 g of graphene for 15 minutes by using a ball mill, calcining for 2 hours in a tubular furnace with nitrogen flow at 300 ℃, cooling the tubular furnace to room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the product containing CuN2O2The yield of the unit carbon material is 56-80%.
Example 3
1) Containing CoN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 1 g of precursor Co-Salen and 1 g of commercial acetylene black for 15 minutes by using a ball mill, calcining for 2 hours in a 300-DEG C tube furnace with nitrogen flow, after the tube furnace is cooled to room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the powder containing the CoN2O2The yield of the unit carbon material is 56-80%.
Example 3
1) Containing CoN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 1 g of precursor Co-Salen and 1 g of commercial acetylene black for 15 minutes by using a ball mill, calcining for 2 hours in a 900 ℃ tubular furnace with nitrogen flow, after the tubular furnace is cooled to room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the powder containing the CoN2O2The yield of the unit carbon material is 56-80%.
Example 4
1) Containing CoN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 1 g of precursor Co-Salen and 1 g of commercial acetylene black for 15 minutes by using a ball mill, calcining the mixture in a tube furnace with the temperature of 900 ℃ and introduced with nitrogen airflow for 12 hours, cooling the tube furnace to the room temperature, washing the obtained black powder with 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and heating the washed black powderDrying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the product containing CoN2O2The yield of the unit carbon material is 56-80%.
Example 5
1) Containing CoN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 10 g of precursor Co-Salen and 10 g of commercial acetylene black for 60 minutes by using a ball mill, calcining for 12 hours in a tube furnace with 900 ℃ introduced with nitrogen airflow, after the tube furnace is cooled to room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven with the temperature of 60 ℃ to obtain the powder containing the CoN2O2The yield of the unit carbon material is 56-80%.
Example 6
1) Containing FeN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 10 g of precursor Fe-Salen and 10 g of commercial acetylene black for 60 minutes by using a ball mill, calcining for 12 hours in a tube furnace with the temperature of 900 ℃ and introduced with nitrogen airflow, after the tube furnace is cooled to the room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven with the temperature of 60 ℃ to obtain the FeN-containing material2O2The yield of the unit carbon material is 56-80%.
Example 7
1) Containing NiN2O2The preparation method of the unit carbon material comprises the following steps: ball-milling 10 g of precursor Ni-Salen and 10 g of commercial acetylene black for 60 minutes by using a ball mill, calcining for 12 hours in a tube furnace with the temperature of 900 ℃ and introduced with nitrogen airflow, after the tube furnace is cooled to the room temperature, washing the obtained black powder by using 30% hydrogen peroxide, deionized water and absolute ethyl alcohol, and drying for 12 hours in a vacuum drying oven with the temperature of 100 ℃ to obtain the NiN-containing material2O2The yield of the unit carbon material is 56-80%.
And (4) performance testing:
(1) The detection method comprises the following steps:
electrochemical nitric oxide detection process: detecting solution phase oxidationDuring nitrogen, silver wire is selected as a counter electrode, carbon is selected as the counter electrode, and the working electrode contains MN2O2A carbon material of the unit. The electrolyte was a deoxygenated PBS solution containing nitric oxide at various concentrations. The nitric oxide solution with different concentrations is detected by adopting a cyclic voltammetry method and a timing voltage method, wherein the test voltage range of the cyclic voltammetry technology is 0.1-1.1V, and the voltage value of the timing voltage is +0.83V. The nitric oxide solution of saturated concentration was prepared from nitric oxide of 99.99% purity by passing it through a saturated deoxygenated PBS solution for 30 minutes. The initial concentration was 1.8mM, and other concentrations were obtained by dilution of 1.8mM of the initial solution. When detecting nitric oxide in human exhaled breath, the collected nitric oxide samples with different concentrations are introduced into the PBS solution at the speed of 50mL/s, and the change of the current value is detected in real time.
(2) And (3) testing results:
1) The MN-containing compound prepared in example 1 was added2O2The unit carbon material shows better linearity in the nitric oxide concentration range of 10 nM-600 nM (as shown in FIG. 5) when applied to electrochemical detection of solution phase nitric oxide.
2) MN contained in the product obtained in example 12O2When the unit carbon material is applied to the electrochemical method for detecting nitric oxide in human exhaled breath, the detection of nitric oxide can be detected at 8ppb (as shown in figure 6).
3) The precursor Ni-Salen prepared in example 1 above and containing MN2O2When the unit carbon material is applied to electrochemical method for detecting nitric oxide of 8ppb in human exhaled air, ni-Salen basically has no response when the detection times reach 20 times, and MN is contained2O2The response value of the unit carbon material (Ni-SAS) is as high as 381.08 (shown in figure 7), and the MN provided by the invention2O2The unit carbon material can have excellent detection sensitivity after being repeatedly used for many times according to the self-heterogeneous property.
4) The precursor Ni-Salen and NiN-containing precursor prepared in example 1 above were mixed2O2Application of unit carbon material in electrochemical method for detecting nitric oxide in 1.8nM solution phaseWhile Ni-Salen is non-responsive and NiN is present2O2The unit carbon material shows obvious response peak (shown in figure 8), which shows that relative to the precursor Ni-Salen, the NiN-containing carbon material provided by the invention2O2The unit carbon material has higher detection sensitivity.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. Containing MN2O2Use of a carbon material of a cell for detecting nitric oxide, characterized in that: the application is as follows:
(1) Detecting nitric oxide in human exhaled breath;
(2) Detecting nitric oxide in the solution phase;
the said MN2O2The preparation method of the unit carbon material comprises the following steps:
ball-milling a precursor M-Salen and a carbon material according to a certain proportion and calcining at high temperature to prepare the Mn-containing material2O2A unit carbon material;
the carbon materials include commercial carbon materials and carbon materials prepared by conventional experimental techniques;
the mass ratio of the precursor M-Salen to the carbon material is 1-100;
the calcination is carried out at high temperature, the calcination temperature is 200-900 ℃, and the calcination time is 1-12 hours.
2. The MN-containing of claim 12O2Use of a carbon material of a unit for detecting nitric oxide, characterized in that: the carbon material is one or more of acetylene black, carbon black, graphene and carbon nano tubes.
3. The MN-containing of claim 12O2Carbon of unitThe application of the material in detecting nitric oxide is characterized in that: the mass ratio of the precursor M-Salen to the carbon material is 1.
4. The MN-containing of claim 12O2Use of a carbon material of a cell for detecting nitric oxide, characterized in that: the calcining temperature is 300-900 ℃, and the calcining time is 2-3 hours.
5. The MN-containing of claim 12O2Use of a carbon material of a cell for detecting nitric oxide, characterized in that: the said MN2O2The preparation method of the unit carbon material comprises the following steps:
mixing and ball-milling a precursor M-Salen and a carbon material according to the mass ratio of 1-100, putting the mixture into a tube furnace, introducing inert gas into the mixture, and calcining the mixture at 200-900 ℃ for 1-12 hours to obtain the Mn-containing material2O2A unit carbon material.
6. The MN-containing of claim 12O2Use of a carbon material of a cell for detecting nitric oxide, characterized in that: the preparation method of the precursor M-Salen comprises the following steps: taking salicylaldehyde, metal salt and amine compound as organic ligands and absolute ethyl alcohol as a reaction solvent to react to prepare the MN2O2Precursor M-Salen of carbon material.
7. The MN-containing of claim 62O2Use of a carbon material of a cell for detecting nitric oxide, characterized in that: the metal salt is acetate, chloride, perchlorate, sulfate, nitrate or diethyl salt.
8. The MN of claim 62O2Use of a carbon material of a cell for detecting nitric oxide, characterized in that: the amine compound is ethylenediamine, cyclohexanediamine or phenylenediamine.
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