CN114778614B - A conductive MOF modified gas-sensitive material and its preparation method and application - Google Patents
A conductive MOF modified gas-sensitive material and its preparation method and application Download PDFInfo
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
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- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical group C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 description 1
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/08—Measuring devices for evaluating the respiratory organs
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
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Abstract
本申请属于传感器材料制备技术领域，本申请提供了一种导电MOF修饰气敏材料及其制备方法和应用，所述导电MOF修饰气敏材料包括：石墨烯组装材料和其表面修饰的导电金属有机框架材料；所述石墨烯组装材料具有二维层状结构，由聚阳离子电解质与带负电的氧化石墨烯组装得到。其制备方法包括：在液相中，将聚阳离子电解质如聚二烯丙基二甲基氯化铵与带负电的氧化石墨烯进行初组装，之后引入导电金属有机框架材料对其进行表面修饰处理，即得。本发明提供的复合气敏材料对于0‑98％宽范围湿度的气体响应稳定性较好，可在室温下实现痕量有机、无机挥发性化合物的选择性检测，应用前景良好。The present application belongs to the technical field of sensor material preparation, and provides a conductive MOF-modified gas-sensitive material and its preparation method and application. The conductive MOF-modified gas-sensitive material includes: a graphene assembly material and a conductive metal organic framework material modified on its surface; the graphene assembly material has a two-dimensional layered structure, which is assembled from a polycation electrolyte and a negatively charged graphene oxide. The preparation method includes: in a liquid phase, a polycation electrolyte such as polydiallyldimethylammonium chloride is initially assembled with a negatively charged graphene oxide, and then a conductive metal organic framework material is introduced to perform surface modification treatment on the polycation electrolyte. The composite gas-sensitive material provided by the present invention has good gas response stability in a wide range of humidity from 0 to 98%, and can achieve selective detection of trace organic and inorganic volatile compounds at room temperature, and has good application prospects.
Description
Technical Field
The application belongs to the technical field of sensor material preparation, and particularly relates to a conductive MOF modified gas-sensitive material, and a preparation method and application thereof.
Background
Metal Organic Frameworks (MOFs) are a new class of nanoporous crystalline materials formed by coordination of metal cations and organic linkers. The material has larger internal porosity, specific surface area and excellent reversible adsorption property, and the changeable pore size and surface environment can provide advantages for the selectivity and the sensitivity of gas sensing. The existence of the polar metal center and the nonpolar organic connecting part in the MOFs structure ensures that the MOFs structure has the capability of selectively adsorbing inorganic and organic volatile gas molecules. Most three-dimensional metal-organic frame materials are insulating materials, however, because of their insulating properties, it is difficult to construct a commonly used chemiresistive gas sensor.
Today, insulated MOFs are used for gas sensing and have been adapted for Surface (SAW) acoustic wave sensors, quartz Crystal Microbalances (QCM), impedance sensors, and capacitive gas sensors (Sensors and Actuators B:chemical,2019, 278:153-164.). Few two-dimensional MOF materials have good conductivity, such as M-HHTP, M-HITP metal organic framework materials (chem.com., 2018, 54, 7873-7891) made with HHTP (2, 3,6,7, 10, 11-hexahydrotriphenylene), HATP.6 HCl (triphenylene-2, 3,6,7, 10, 11-hexamine hexahydro-chloride), and the like as organic ligands. Such 2D MOF materials can be directly prepared into chemi-resistive gas sensors or sensor arrays (j.am. Chem. Soc.2015, 137, 13780-13783;Sensors 2017, 17, 2192) due to their specific electrical properties.
However, reported single MOF material composition gas sensors detect different gases at essentially ppm (10 -6) levels (chem. Commun.,2018, 54, 7873-7891), which hinders the gas detection requirements at lower levels they need to reach in practical applications. Ming-ShuiYao et al used Cu 3(HHTP)2 to detect NH 3 at 100ppm with response and recovery times of 1.36min and 9.11min (Angew. Chem.2017, 129, 16737-16741), thus demonstrating that a single conductive MOF material may be difficult to achieve with the goal of trace rapid detection of analyte gases.
Disclosure of Invention
In view of the above, the application provides a conductive MOF modified gas-sensitive material, a preparation method and application thereof, and the gas-sensitive material can realize the selective detection of trace organic and inorganic volatile compounds at room temperature.
The invention provides a conductive MOF modified gas-sensitive material which can be used for reducing the influence of humidity in a gas detection process, wherein the conductive MOF modified gas-sensitive material comprises a graphene assembly material and a conductive metal-organic framework material with a modified surface;
the graphene assembly material has a two-dimensional layered structure and is assembled by polycation electrolyte and negatively charged graphene oxide.
The invention provides a preparation method of a conductive MOF modified gas-sensitive material, which comprises the following steps:
in a liquid phase, a polycation electrolyte such as polydiallyl dimethyl ammonium chloride and negatively charged graphene oxide are initially assembled, and then a conductive metal organic framework material is introduced to carry out surface modification treatment on the polycation electrolyte, so that the conductive MOF modified gas-sensitive material is obtained.
In the embodiment of the invention, the molecular weight of the polydiallyl dimethyl ammonium chloride is 200-350kDa; preferably, 10-60. Mu.L of a 1wt% strength polydiallyl dimethyl ammonium chloride solution is added to 0.5mL of graphene oxide solution for initial assembly.
In the embodiment of the invention, after the initial assembly, adding a conductive metal organic frame material suspension with the same volume as that of the graphene oxide solution, and realizing surface modification by oscillation; the conductive metal organic framework material includes, but is not limited to Co3(HITP)2、Ni3(HITP)2、Cu3(HITP)2、Co3(HHTP)2 or Cu 3(HHTP)2.
The invention provides a gas sensing chip which is prepared by combining the conductive MOF modified gas-sensitive material and an electrode.
In an embodiment of the present invention, the substrate of the electrode is a flexible substrate or a hard substrate, and the flexible substrate is preferably a PET film, a PEN film, a PI film or a PC film; the rigid substrate is preferably silicon, glass, ceramic or a PCB board.
The invention provides a preparation method of a gas sensing chip, which comprises the following steps:
step one, preparing the self-assembled suspension of the conductive MOF modified gas-sensitive material;
Step two, limiting the domain of the ITO-PET interdigital electrode by using a PDMS film, treating the electrode by using oxygen plasma, then dripping the self-assembled suspension of the conductive MOF modified gas-sensitive material prepared in the step one into an electric limiting domain, and drying at room temperature; and (3) placing the dried electrode in a reducing vapor atmosphere for reduction to obtain the gas sensing chip.
The invention provides an application of the gas sensing chip in gas detection.
In an embodiment of the invention, the gas detection is the detection and identification of different organic/inorganic gases and exhaled breath of the human body.
In the embodiment of the invention, the carrier gas adopted in the gas detection is background gas of the sample gas; the sample gas is an organic, inorganic volatile gas including, but not limited to, nitric oxide, nitrogen dioxide, hydrogen sulfide, ammonia, acetone, isoprene, or water vapor.
In an embodiment of the invention, the conditions of the gas detection meet at least one of the following: the gas concentration is 0.1-10ppm, the room temperature and the different humidity are 0-98%.
In the embodiment of the invention, the Co 3(HITP)2 surface modified gas sensitive material is used for detecting nitric oxide and nitrogen dioxide.
A single three-dimensional insulating MOF cannot construct a chemiresistive gas sensor, whereas a single conductive MOF is typically tested at ppm level when testing gas, e.g. Cu 3(HHTP)2 is tested at 1ppm-100 ppm.
Compared with the prior art, the invention provides a conductive MOF modified gas-sensitive material which is a graphene gas sensing material with a modified surface and is mainly formed by compounding a graphene assembly material and a conductive metal organic framework material with a modified surface, wherein the graphene assembly material has a two-dimensional layered structure and is assembled by polycation electrolyte and negatively charged graphene oxide. According to the embodiment of the invention, the polycation electrolyte PDDA is adopted to intercalate the negatively charged two-dimensional material graphene, the initial assembly of PDDA and graphene is realized through electrostatic self-assembly, the problem that graphene is easy to self-aggregate in a solution can be solved, and on the basis, a conductive metal organic framework Material (MOF) is introduced to carry out further surface modification on the graphene, so that the stable assembly of the material in a liquid phase can be realized. Namely, the invention adopts the conductive MOF to modify the graphene to obtain the gas-sensitive material, further increases the specific surface area and pores of the graphene, is beneficial to gas adsorption, diffusion and desorption, improves the detection sensitivity of various gases, and realizes the selective detection of trace organic and inorganic volatile gases at room temperature.
Furthermore, the invention adopts the conductive MOF containing the hydrophobic aryl to modify the graphene gas-sensitive material, which is the gas-sensitive material introduced with the hydrophobic aryl, can reduce the influence of humidity factors on gas detection, and provides a foundation for the subsequent application of the gas-sensitive material in practical application.
Further, the invention adopts two-dimensional conductive MOF to modify graphene gas-sensitive material. Because the three-dimensional conductive MOF is not well dispersed in the aqueous solution required by the experimental protocol, whereas the two-dimensional conductive MOF can be achieved.
Reducing the impact of humidity factors on gas detection is also critical in developing gas sensors. At present, it has been reported that indium selenide, indium oxide, tungsten oxide and the like can be used as gas sensitive materials (most of which are MO or MO-containing composite/doped materials) to prepare effective moisture-resistant photoelectric gas sensors, resistive gas sensors and the like (Anal.Chem.2020,92,11277-11287;IEEE SENSORS JOURNAL,VOL.21,NO.8,APRIL 15,2021;Sensors and Actuators：B.Chemical 350(2022)130884), which are only slightly affected when subjected to gas detection in a humidity fluctuation range, but detection often requires exposure to light (such as UV or infrared) or high temperature (such as 275 ℃) and prevents the detection from being carried out under the conditions of no light assistance and room temperature.
The MOF is modified on the surface of the graphene-based gas-sensitive material, so that the problem can be solved, the composite gas-sensitive material provided by the invention can obtain a relatively stable response value and relatively high sensitivity for the gas with the wide humidity range of 0-98% under the room temperature and no other auxiliary conditions, the selective detection of trace (ppb level) organic/inorganic volatile compounds is realized, the complex expiration detection requirement is met, and the composite gas-sensitive material can be further applied to a gas detection device, and the disease identification and health management related to expiration are realized.
Drawings
FIG. 1 is a scanning electron microscope image of a graphene oxide/PDDA/Co 3(HITP)2 gas sensing material described in example 2; wherein a structural schematic of Co 3(HITP)2 with a hydrophobic aryl group is attached;
FIG. 2 is a C1s spectrum of a graphene oxide/PDDA/Co 3(HITP)2 gas sensing material described in example 2;
FIG. 3 is a N1s spectrum of a graphene oxide/PDDA/Co 3(HITP)2 gas sensing material described in example 2;
FIG. 4 is a graph showing the response kinetics of the graphene oxide/PDDA/Co 3(HITP)2 gas sensitive material described in example 3 to different gases under a concentration gradient;
FIG. 5 is a graph comparing the response results of the graphene oxide/PDDA/Co 3(HITP)2 gas sensitive material described in example 3 to six different gases at a concentration of 1ppm or 2 ppm; wherein the gas comprises: 1ppm (NO, NO 2、H2S、NH3, ace), 2ppm (Iso);
FIG. 6 is a graph comparing the response kinetics of graphene oxide/PDDA/Co 3(HITP)2 gas sensitive materials described in example 4 to nitric oxide, nitrogen dioxide gases at a concentration gradient of 0.1-1 ppm; the contrast material is a graphene oxide/Co 3(HITP)2, graphene oxide/PDDA material;
FIG. 7 is a graph showing the comparison of the response of the graphene oxide/PDDA/Co 3(HITP)2 gas sensitive material described in example 5 to nitric oxide gas at 200ppb concentrations at different humidities;
FIG. 8 is a graph of the relative response variation of FIG. 7;
FIG. 9 is a schematic view of the exhaled breath and ambient air collection device of example 6;
fig. 10 is a graph showing the detection and identification result of exhaled gas at room temperature of the graphene oxide/PDDA/Co 3(HITP)2 gas sensitive material described in example 6.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application provides a conductive MOF modified gas-sensitive material, which comprises a graphene assembly material and a conductive metal organic framework material with a modified surface; the graphene assembly material has a two-dimensional layered structure and is assembled by polycation electrolyte and negatively charged graphene oxide, and the conductive MOF modified gas-sensitive material can be used for reducing the influence of humidity in the gas detection process.
The gas-sensitive material provided by the invention has the characteristics of good pore structure and the like, is favorable for gas adsorption, diffusion and desorption, improves the detection sensitivity of various gases, and can realize the selective detection of trace organic and inorganic volatile compounds at room temperature.
The graphene material has the characteristics of high specific surface area, strong electron transmission capability, adjustable energy band, high flexibility and the like while maintaining certain mechanical strength, so that the graphene material has great advantages in gas sensing, and the graphene-based composite gas-sensitive material can detect gas at ppb (10 -9) level. However, the conventional graphene oxide is unstable in a liquid phase and is easy to self-polymerize, so that the sensitivity of the sensing material is reduced.
It has been reported that complexing negatively charged graphene oxide with some polycationic electrolytes (PDDA, PAH, PEI, etc.) can prevent agglomeration, improve gas accessibility, and both LinWang et al and PingNi et al assemble graphene oxide with polycationic electrolyte PDDA, thereby maintaining a graphene oxide layered system (Separation and Purification Technology (2016) 123-131, carbon48 (2010) 2100-2105). There are also reports that the MOF material can be compounded with graphene to obtain a good gas sensing material, wherein most of the MOF material is three-dimensional insulating MOF, common MOFs include Cu-BTC、Zn-MOF(Materials Research Bulletin 99(2018)152-160,Journal of Alloys and Compounds 816(2020)152509) and the like, and few reports of the MOF material compounded with two-dimensional conductive MOFs for gas sensing are provided. In the liquid phase, the conductive MOF material and the graphene oxide are difficult to stably assemble, and the sensitivity is low when trace gases are detected.
The conductive MOF modified gas-sensitive material provided by the invention is a novel multi-element composite material obtained by compositing conductive MOF material with graphene and other gas sensing materials.
In the composite gas-sensitive material provided by the embodiment of the invention, the main body is a graphene assembly material with a two-dimensional layered structure, and the composite gas-sensitive material is formed by intercalation of polycation electrolyte PDDA and negatively charged graphene oxide and electrostatic self-assembly; the polycation electrolyte is particularly preferably polydiallyl dimethyl ammonium chloride (PDDA), which is favorable for stable assembly of materials in a liquid phase and room-temperature trace gas detection (especially favorable for improving sensitivity).
In a preferred embodiment of the invention, the polydiallyl dimethyl ammonium chloride has a molecular weight of 200 to 350kDa. In the embodiment of the invention, 10-60 mu L of polydiallyl dimethyl ammonium chloride solution with the concentration of 1wt% is preferably added into 0.5mL of graphene oxide solution for initial assembly; the PDDA solution is preferably used in an amount of 15 to 50. Mu.L, more preferably 20 to 40. Mu.L.
The surface of the graphene assembly material is modified with a conductive MOF material; the metal of the modified conductive MOF material may be cobalt (Co), nickel (Ni), copper (Cu), including but not limited to Co3(HITP)2、Ni3(HITP)2、Cu3(HITP)2、Co3(HHTP)2 or Cu 3(HHTP)2, etc. Illustratively, co 3(HHTP)2: co-HHTP metal organic framework materials are prepared by taking HHTP (2, 3,6,7, 10, 11-hexahydroxytriphenylene) as an organic ligand. The conductive MOF has great advantages in preparing a chemical resistance type gas sensor due to the excellent conductivity of the conductive MOF.
The gas-sensitive material of the conductive MOF modified graphene can be recorded as a graphene oxide/PDDA/MOF composite material and the like, further increases the specific surface area and pores of the graphene, is beneficial to gas adsorption, diffusion and desorption, improves the detection sensitivity of various gases, and realizes the selective detection of trace organic and inorganic volatile gases at room temperature.
In some embodiments of the invention, the composite material has surface folds, a staggered network structure, and a conductive MOF material (carbon-metal bonds, etc.) attached to the surface. The gas-sensitive material provided by the embodiment of the invention has hydrophobic aryl, so that the influence of humidity factors on gas detection can be reduced, and a foundation is provided for the subsequent application of the gas-sensitive material to practical applications.
The embodiment of the invention provides a preparation method of a conductive MOF modified gas-sensitive material, which comprises the following steps:
in a liquid phase, a polycation electrolyte such as polydiallyl dimethyl ammonium chloride and negatively charged graphene oxide are initially assembled, and then a conductive metal organic framework material is introduced to carry out surface modification treatment on the polycation electrolyte, so that the conductive MOF modified gas-sensitive material is obtained.
Further, the invention provides a gas sensing chip which is prepared by combining the conductive MOF modified gas-sensitive material and an electrode.
According to the embodiment of the invention, through a step-by-step assembly strategy, the polycation electrolyte PDDA and the negatively charged graphene oxide are initially assembled in a liquid phase, and then a conductive metal organic framework material is introduced to carry out further surface modification; the invention can be stably assembled in a liquid phase to prepare the gas-sensitive material suspension. According to the invention, through a step-by-step assembly strategy, the problem of liquid phase assembly of a single MOF material and graphene oxide is solved, and stable assembly of the material in a liquid phase and selective detection of trace organic and inorganic volatile compounds at room temperature are realized.
The embodiment of the invention provides a preparation method of a conductive MOF modified gas-sensitive material and a gas sensing chip, which comprises the following steps:
step one, preparing graphene oxide/PDDA/MOF self-assembled suspension:
Adding a trace of PDDA into a certain amount of graphene oxide solution, oscillating uniformly, preferably adding MOF suspension with the same volume as the graphene oxide solution, oscillating overnight on an oscillating instrument, centrifugally washing for 3 times by using deionized water, and redispersing by using the same volume of deionized water to obtain the nano-particle.
According to the invention, the sensing material is assembled step by step, and the conductive MOF material and the graphene oxide are assembled in the liquid phase in an auxiliary manner by PDDA, so that the self-aggregation problem of the graphene oxide and the assembly problem of a single MOF material and the graphene oxide are overcome, and the stable assembly of the material in the liquid phase is realized.
Preferably, the molecular weight Mw of the PDDA is from 200 to 350kDa. In the embodiment of the invention, 10-60 mu L of polydiallyl dimethyl ammonium chloride solution with the concentration of 1wt% is added into 0.25-0.75mL of graphene oxide solution for initial assembly, preferably 0.5mL; the PDDA solution is preferably used in an amount of 15 to 50. Mu.L, more preferably 20 to 40. Mu.L, and still more preferably 20. Mu.L. In addition, the concentration of the graphene oxide solution may be 0.25 to 1.0mg/mL, preferably 0.5mg/mL.
Specifically, the MOF suspension is a suspension obtained by dispersing conductive MOF materials in deionized water by ultrasonic waves, and the conductive MOF materials include, but are not limited to Co3(HITP)2,Ni3(HITP)2,Cu3(HITP)2,Co3(HHTP)2,Cu3(HHTP)2 and the like.
Preparing a graphene oxide/PDDA/MOF material gas sensing chip:
the ITO-PET interdigital electrode can be limited by a PDMS film (the PDMS film is also called as a polydimethylsiloxane film), and the electrode is treated by oxygen plasma;
And then, dripping the PDDA-assisted graphene oxide and metal organic frame material self-assembled suspension (graphene oxide/PDDA/MOF self-assembled suspension) prepared in the step one into an electric limit area, dripping the suspension into the electric limit area, preferably drying the suspension at room temperature with the dosage of 5-10 mu L, preferably 10 mu L, and then placing the electrode in a gas atmosphere of 70-120 ℃ reducing vapor for reduction for 15-30 min to obtain the graphene oxide/PDDA/MOF material gas sensing chip (gas sensing chip).
In some embodiments of the present invention, the substrate may have a thickness that is appropriate, and may be: flexible substrates such as PET (polyethylene terephthalate) film, PEN (polyethylene naphthalate) film, PI (polyimide) film, PC (polycarbonate) film, and the like, and rigid substrates such as silicon, glass, ceramics, and PCB (printed circuit board) may be used.
In addition, the reducing vapor includes, but is not limited to, hydrazine hydrate.
In the preparation of the aforementioned conductive MOF-modified gas-sensitive material, in the first step of an embodiment, the preparation process of the graphene oxide/PDDA/Co 3(HITP)2 self-assembled suspension is preferably as follows:
mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Co 3(HITP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water to give graphene oxide/PDDA/Co 3(HITP)2 self-assembled suspension.
In the preparation of the aforementioned conductive MOF-modified gas-sensitive material, in the first step of an embodiment, the preparation process of the graphene oxide/PDDA/Ni 3(HITP)2 self-assembled suspension is preferably as follows:
mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Ni 3(HITP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water to give graphene oxide/PDDA/Ni 3(HITP)2 self-assembled suspension.
In the preparation of the conductive MOF modified gas sensitive material, in the first step of an embodiment, the preparation process of the graphene oxide/PDDA/Cu 3(HITP)2 self-assembled suspension is as follows:
mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Cu 3(HITP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water to give a graphene oxide/PDDA/Cu 3(HITP)2 self-assembled suspension.
In the preparation of the aforementioned conductive MOF-modified gas-sensitive material, in the first step of an embodiment, the preparation process of the graphene oxide/PDDA/Co 3(HHTP)2 self-assembled suspension is preferably as follows:
mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Co 3(HHTP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water to give graphene oxide/PDDA/Co 3(HHTP)2 self-assembled suspension.
In the preparation of the conductive MOF modified gas sensitive material, in the first step of an embodiment, the preparation process of the graphene oxide/PDDA/Cu 3(HHTP)2 self-assembled suspension is as follows:
mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Cu 3(HHTP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water to give a graphene oxide/PDDA/Cu 3(HHTP)2 self-assembled suspension.
Meanwhile, the invention also provides application of the gas sensing chip in gas detection, and can provide a gas detection device which comprises the gas sensing chip, a connected gas acquisition unit, a display unit and the like. In an embodiment of the invention, the gas detection is the detection and identification of different organic/inorganic gases and exhaled breath of the human body. Preferably, the conditions for gas detection according to the present invention satisfy at least one of the following: the gas concentration is 0.1-10ppm, the room temperature and the different humidity are 0-98%.
The conductive MOF modified gas-sensitive material provided by the embodiment of the invention can be used for detecting and identifying gas at room temperature, and the application method is as follows:
Placing the graphene gas sensing chip modified by the conductive MOF in a gas flow cell, firstly introducing carrier gas until a base line tends to be stable in the test process, then introducing sample gas at the same flow rate, and testing the current value flowing through the gas-sensitive material by a picoampere meter under a given voltage to obtain data of the relation between the current value and time, thereby enabling the gas-sensitive material to respond to different gases;
Wherein the carrier gas is a background gas of the sample gas; the sample gas may be an organic, inorganic volatile gas including, but not limited to, nitric Oxide (NO), nitrogen dioxide (NO 2), hydrogen sulfide (H 2 S), ammonia (NH 3), acetone, isoprene, water vapor (H 2 O), and the like.
The response value may be defined as R% = [ (I-I 0)/I0 ] ×100, where I is a current value measured under a sample gas atmosphere, and I 0 is a current value measured under a carrier gas atmosphere.
The conductive MOF modified gas-sensitive material can be used for detecting gas under different humidity, and the application method is as follows:
Placing the graphene gas sensing chip modified by the conductive MOF in a gas flow cell, introducing carrier gas until a base line tends to be stable in the test process, then introducing dry sample gas or wet sample gas after passing through different saturated salt solutions at the same flow rate, and testing the current value flowing through the gas sensitive material by a picometer under a given voltage to obtain data of the relation between the current value and time, thereby obtaining response images of the gas sensitive material to the sample gas under different humidity;
Wherein the carrier gas is a background gas of the sample gas; the saturated salt solution includes, but is not limited to, saturated potassium acetate solution, saturated magnesium nitrate solution, saturated sodium chloride solution, saturated potassium sulfate solution, and the like. The sample gas is an organic and inorganic volatile gas, including but not limited to gases which are difficult to dissolve in water, such as nitric oxide, acetone, isoprene and the like.
The response value may be defined as R% = [ (I-I 0)/I0 ] ×100, where I is a current value measured under a dry or wet sample gas atmosphere and I 0 is a current value measured under a carrier gas atmosphere.
The conductive MOF modified gas-sensitive material can detect and identify mixed gas (exhaled air of human body) at room temperature, and the application method is as follows:
Placing the conductive MOF modified graphene gas sensing chip in a gas flow cell, firstly introducing pretreated environmental gas until a base line tends to be stable in the test process, then introducing pretreated human body exhaled gas at the same flow rate, and testing the current value flowing through a gas-sensitive material by a picometer under a given voltage to obtain data of the relation between the current value and time, wherein the data can be used for identifying the gas according to the response value difference analysis of different introduced mixed gases (human body exhaled gas);
The human exhaled air is exhaled air of healthy individuals and exhaled air of patients with simulated airway inflammatory diseases, wherein the airway inflammatory diseases include, but are not limited to, airway inflammatory diseases such as asthma, chronic Obstructive Pulmonary Disease (COPD) and the like; the exhaled gas of the patient with the simulated airway inflammatory disease is achieved by introducing a quantitative standard gas into the exhaled gas of the healthy individual.
In some embodiments of the invention, the pretreatment is performed by immersing the gas through a Teflon hard tube of inner diameter 4-8mm with 20-40cm in ice water.
The response value may be defined as R% = [ (I-I 0)/I0 ] ×100, where I is a current value measured under a mixed gas atmosphere, and I 0 is a current value measured under an ambient gas atmosphere.
In summary, the invention provides a conductive MOF modified gas-sensitive material, a preparation method and application thereof, and PDDA and graphene oxide are preferably initially assembled and then are modified by introducing the conductive MOF material, so that detection and identification of different organic/inorganic gases and human exhaled gases (such as exhaled gases of patients suffering from airway inflammatory diseases) are realized. The composite material provided by the invention can realize the selective detection of trace (ppb level) organic/inorganic volatile compounds at room temperature, and has good sensitivity.
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention. The examples of the present invention use commercially available materials. Wherein, the graphene oxide (10 mg/mL) is produced by the method that the manufacturer is the national academy of sciences of organic chemistry, inc., and the MOF material is a reference, and the specific surface area is larger, for example, co 3(HITP)2 is about 805.5m 2/g、Ni3(HITP)2 is about 884.7m 2/g. The reducing vapor is hydrazine hydrate.
Example 1:
The embodiment mainly provides a preparation method of graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive materials with different PDDA contents, and selects the PDDA content with the optimal proportion, which comprises the following specific steps:
step one, preparing graphene oxide/PDDA/Co 3(HITP)2 self-assembled suspension: 10. Mu.L, 20. Mu.L, 30. Mu.L, 40. Mu.L and 60. Mu.L PDDA (Mw.200-350 kDa,1% wt.) were added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Co 3(HITP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water, to give graphene oxide/PDDA/Co 3(HITP)2 self-assembled suspensions, respectively.
Preparing graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive chips with different PDDA contents: and (3) limiting the domain of the ITO-PET interdigital electrode by using a PDMS film, treating the electrode by using oxygen plasma (the oxygen plasma treatment time is 30 s), and then respectively taking 10 mu L of the suspension liquid prepared in the step one and prepared by self-assembling the 5 PDDA auxiliary graphene oxide and the MOF material, dropwise adding the suspension liquid into the electric limiting domain, and drying at room temperature. And (3) placing the electrode in a reducing vapor atmosphere at 70 ℃ for reducing for 20-30 min to obtain the graphene oxide/PDDA/MOF gas sensing chip with different PDDA contents.
As an example, the graphene oxide/PDDA/Co 3(HITP)2 gas sensor chips with 5 different PDDA contents prepared above were used for detecting nitric oxide, wherein when the PDDA content is 20 μl, the sensitivity of graphene oxide/PDDA/Co 3(HITP)2 is optimal when detecting gas.
Example 2:
the embodiment mainly provides a preparation method of a graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material, which comprises the following specific steps:
Step one, preparing graphene oxide/PDDA/Co 3(HITP)2 self-assembled suspension: mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 0.5mL of graphene oxide solution (0.5 mg/mL), after shaking uniformly, 0.5mL of Co 3(HITP)2 (0.5 mg/mL) suspension was added, shaking overnight on a shaker, followed by centrifugation wash 3 times with deionized water and redispersion with equal volumes of deionized water to give graphene oxide/PDDA/Co 3(HITP)2 self-assembled suspension.
Preparing a graphene oxide/PDDA/Co 3(HITP)2 gas sensing chip: and (3) limiting the domain of the ITO-PET interdigital electrode by using a PDMS film, treating the electrode for 30s by using oxygen plasma, then dripping 10 mu L of PDDA-assisted graphene oxide and MOF material self-assembled suspension prepared in the step one into an electric limit domain, and drying at room temperature. And (3) placing the electrode in a reducing vapor atmosphere at 70 ℃ for 20min to obtain the graphene oxide/PDDA/MOF material gas sensing chip.
The scanning electron microscope image of the graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material with the PDDA content of 20 mu L is shown in fig. 1, and folds, staggered net structures and Co 3(HITP)2 attached to the surface of the composite material can be observed, so that the composite material is proved to be compounded and the structure is favorable for gas sensing. X-ray photoelectron spectroscopy C1s and N1s of the graphene oxide/PDDA/Co 3(HITP)2 gas sensitive material with PDDA content of 20 mu L are shown in figure 2 and figure 3. The existence of C-Co bonds observed by the C1s spectrogram of the composite material proves that the material is compounded, and the N1s spectrogram peak corresponds to the integral composition of the material.
In addition, other MOF modified composite materials were prepared in accordance with this example without special steps.
Example 3:
The following specific description is made on detection and identification of organic/inorganic volatile compounds at room temperature for the graphene oxide/PDDA/Co 3(HITP)2 gas sensor chip prepared in the above example 2, which is a conductive MOF-modified graphene gas sensor material:
As an example, the graphene oxide/PDDA/Co 3(HITP)2 gas sensor chip prepared in example 2 was used for detection of nitric oxide/nitrogen dioxide/hydrogen sulfide/ammonia gas/isoprene/acetone: and placing the graphene oxide/PDDA/Co 3(HITP)2 gas sensing chip in a gas flow cell, firstly introducing carrier gas until a base line tends to be stable in the test process, then introducing nitric oxide, nitrogen dioxide, hydrogen sulfide, ammonia, isoprene or acetone with different concentrations at the same flow rate, and testing the current value flowing through the gas sensitive material through a picoammeter at 1V voltage to obtain data of the relation between the current value and time. The response values of the graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material to different gases with different concentrations can be known.
The kinetics of the detection of the nitric oxide standard gas at 0.1-1ppm is shown in FIG. 4a, the kinetics of the detection of the nitrogen dioxide standard gas at 0.1-1ppm is shown in FIG. 4b, the kinetics of the detection of the hydrogen sulfide standard gas at 0.1-1ppm is shown in FIG. 4c, the kinetics of the detection of the ammonia standard gas at 1-10ppm is shown in FIG. 4d, the kinetics of the detection of the isoprene standard gas at 2-10ppm is shown in FIG. 4e, and the kinetics of the detection of the acetone standard gas at 1-10ppm is shown in FIG. 4 f. The fundamental trend of the above kinetic profile is to exhibit a linear increase at low concentrations and to saturate at high concentrations.
The detection results of the graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material on six gases are shown in figure 5, and the sensitivity of the graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material on nitric oxide and nitrogen dioxide is higher than that of the other four gases under the conditions of 1ppm of nitric oxide, 1ppm of nitrogen dioxide, 1ppm of hydrogen sulfide, 1ppm of ammonia, 2ppm of isoprene or 1ppm of acetone, which indicates that the conductive MOF modified graphene gas-sensitive material has certain selectivity on different gases.
Example 4:
the following specific description is made on the advantages of the graphene gas-sensitive material modified by the conductive MOF compared with the single-element and binary composite material in detecting nitrogen oxides at room temperature by testing a single graphene oxide, a graphene oxide/Co 3(HITP)2 binary composite material chip, a graphene oxide/PDDA binary composite material chip and the graphene oxide/PDDA/Co 3(HITP)2 gas sensing chip prepared in the above embodiment 2:
As an example, a single graphene oxide material, a graphene oxide/Co 3(HITP)2 binary composite material, a graphene oxide/PDDA binary composite material, and the graphene oxide/PDDA/Co 3(HITP)2 gas sensing material prepared in the above example 2 were used for detecting nitric oxide/nitrogen dioxide gas, respectively: and (3) placing a single graphene oxide chip, a graphene oxide/Co 3(HITP)2 binary composite material chip, a graphene oxide/PDDA binary composite material chip and a graphene oxide/PDDA/Co 3(HITP)2 gas sensing chip in a gas flow cell in a separated mode, introducing carrier gas until a baseline tends to be stable in the test process, introducing nitric oxide or nitrogen dioxide with different concentrations at the same flow rate, and testing the current value flowing through the gas sensitive material through a picoampere meter at 1V voltage to obtain data of the relation between the current value and time. From this, it can be seen that the response values of the single graphene oxide material, the graphene oxide/Co 3(HITP)2 binary composite material, the graphene oxide/PDDA binary composite material, and the graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material to different gases with different concentrations.
The dynamic curve of the detection of the nitrogen monoxide standard gas of 0.1-1ppm by the four different materials is shown in a graph 6a, the dynamic curve of the detection of the nitrogen dioxide standard gas of 0.1-1ppm is shown in a graph 6b, the sensitivity of the graphene oxide/PDDA/Co 3(HITP)2 gas-sensitive material to nitrogen monoxide and nitrogen dioxide is far higher than that of other three single-element and binary materials, and the conductive MOF modified graphene gas-sensitive material has certain advantages in the aspect of detecting nitrogen oxides compared with the single-element and binary composite materials at room temperature.
The preparation method of the graphene oxide, the graphene oxide/Co 3(HITP)2 and the graphene oxide/PDDA material comprises the following specific steps:
Step one: the concentration of the single graphene oxide is 0.5mg/mL, and 1.0mL of graphene oxide solution is taken to be uniformly dispersed by ultrasonic, so that the single graphene oxide material is obtained;
preparing graphene oxide/Co 3(HITP)2 binary material: adding 0.5mL of Co 3(HITP)2 (0.5 mg/mL) suspension into 0.5mL of graphene oxide solution (0.5 mg/mL), oscillating overnight on an oscillator, centrifuging and washing 3 times with deionized water after uniform oscillation, and redispersing with equal volume of deionized water to obtain graphene oxide/Co 3(HITP)2 binary material suspension;
Preparing graphene oxide/PDDA binary material: mu.L of PDDA (Mw.200-350 kDa,1% Wt.) was added to 1.0mL of graphene oxide solution (0.5 mg/mL), shaken overnight on a shaker, after shaking uniformly, centrifugally washed 3 times with deionized water, and redispersed with an equal volume of deionized water to give a graphene oxide/PDDA binary material suspension.
Step two: preparing graphene oxide, graphene oxide/Co 3(HITP)2 and graphene oxide/PDDA sensing chips: and (3) limiting the domain of the ITO-PET interdigital electrode by using a PDMS film, treating the electrode for 30s by using oxygen plasma, and then taking 10 mu L of single graphene oxide, graphene oxide/Co 3(HITP)2 and graphene oxide/PDDA material suspension prepared in the step one, respectively dripping the single graphene oxide, the graphene oxide/Co 3(HITP)2 and the graphene oxide/PDDA material suspension into the electric limiting domain, and drying at room temperature. And (3) placing the electrodes with the different materials dropwise into a reducing vapor atmosphere at 70 ℃ for reduction for 10-30min to obtain the graphene oxide, graphene oxide/Co 3(HITP)2 and graphene oxide/PDDA gas sensing chip.
Example 5:
The following two kinds of composite gas sensor chips, namely graphene oxide/PDDA/Co 3(HITP)2 and graphene oxide/PDDA (prepared in example 4) prepared in example 2, are used for comparing and specifically explaining the detection of nitric oxide gases with different humidity by using graphene gas-sensitive materials before and after modification of conductive MOF:
As an example, the graphene oxide/PDDA/Co 3(HITP)2 and the graphene oxide/PDDA two composite gas sensor chips prepared in example 2 were used for detecting nitric oxide gas under different humidity respectively: and placing the graphene oxide/PDDA/Co 3(HITP)2 or the graphene oxide/PDDA composite gas sensing chip in a gas flow cell, firstly introducing carrier gas until a base line tends to be stable in the test process, then introducing dry nitric oxide gas or wet nitric oxide gas after passing through different saturated salt solutions at the same flow rate, and testing the current value flowing through the gas sensitive material through a picoampere meter under the voltage of 1V to obtain data of the relation between the current value and time. From this, it can be seen that the response values of the graphene oxide/PDDA/Co 3(HITP)2 and the graphene oxide/PDDA composite gas-sensitive material to nitric oxide gas under different humidity conditions.
The results of the measurement of the response of graphene oxide/PDDA and graphene oxide/PDDA/Co 3(HITP)2 to nitric oxide standard gas at 200ppb concentration at 0%,23%,56%,75%,98% humidity are shown in fig. 7a and 7 b. The relative response change values of the two materials to nitric oxide gas under different humidity are shown in figure 8, the response value of the Co 3(HITP)2 after surface modification is nearly doubled, but the ratio of the response value of the Co 3(HITP)2 to the relative 0% under different humidity is smaller than 1.2 and is lower than that of the graphene oxide/PDDA material, so that the graphene oxide/PDDA/Co 3(HITP)2 material is stable in response value to nitric oxide gas with humidity in a wide range of 0% -98%.
According to the invention, the gas-sensitive material is prepared by modifying graphene with conductive MOF, hydrophobic aryl is introduced, and the influence of humidity factors on gas detection is verified to be reduced by comparing the graphene oxide/PDDA binary composite material without MOF material, so that a foundation is provided for the subsequent gas-sensitive material to be used for practical application.
Example 6:
The following specific description is made on the detection and identification of expired gas at room temperature by the graphene oxide/PDDA/Co 3(HITP)2 gas sensor chip prepared in the above-mentioned example 2 for the graphene gas-sensitive material modified by conductive MOF:
As an example, the graphene oxide/PDDA/Co 3(HITP)2 gas sensor chip prepared in example 2 was used for detection and identification of exhaled gas at room temperature-one for the identification of Chronic Obstructive Pulmonary Disease (COPD) patients and healthy individuals: firstly, collecting the exhaled air of a healthy individual with a fasting state or more than 2 hours after meals into a 2L perfluoroethylene propylene copolymer (FEP) sampling bag in a ventilation environment, wherein the exhaled air of a patient with Chronic Obstructive Pulmonary Disease (COPD) is simulated by introducing 25ppb standard nitric oxide gas into the exhaled air of the healthy individual, and simultaneously collecting the local ambient air at the moment into a 10L perfluoroethylene propylene copolymer (FEP) sampling bag as carrier gas; when collecting gas, the gas was first passed through a Teflon hard tube with an inner diameter of 4mm immersed in an ice water bath at 30cm, and the ambient gas and exhaled gas collecting device was as shown in FIG. 9.
Wherein, (a) is a collection device schematic of exhaled air, (b) is a collection device schematic of ambient air, wherein 1 is human exhaled air, 2 is a vital capacity mouthpiece, 3 is an ice water bath, 4 is an air pipeline, 5 is a 2L perfluoroethylene propylene copolymer (FEP) air sampling bag, 6 is ambient air, 7 is a micropump, and 8 is a 10L perfluoroethylene propylene copolymer (FEP) air sampling bag.
The graphene oxide/PDDA/Co 3(HITP)2 gas sensing chip is placed in a gas flow cell, in the test process, pretreated ambient gas is firstly introduced until a base line tends to be stable, then pretreated human body exhaled gas is introduced under the flow rate, under the voltage of 1V, the current value flowing through the graphene oxide/PDDA/Co 3(HITP)2 gas sensing chip is tested through a picometer, the data of the relation between the current value and time is obtained, the identification of different mixed gases can be used according to the difference analysis of the response values of the introduced different mixed gases (human exhaled gas), and the detection and identification results of 15 cases of simulated Chronic Obstructive Pulmonary Disease (COPD) patients and 15 cases of healthy individual exhaled gas are shown in figure 10.
The results show that the response of the exhaled air of the healthy person and the exhaled air of the simulated Chronic Obstructive Pulmonary Disease (COPD) patient are obviously different, and the response values of the two types of gases are obvious in clustering effect, so that the material can realize the detection and identification of mixed gases and provide a feasible basis for the application of the subsequent gas-sensitive material to actual disease samples.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
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