CN108918603B - Porous zinc oxide nanosheet load transition metal doped g-C 3 N 4 Synthesis method of composite gas-sensitive material - Google Patents
Porous zinc oxide nanosheet load transition metal doped g-C 3 N 4 Synthesis method of composite gas-sensitive material Download PDFInfo
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Abstract
The invention relates to a porous zinc oxide nano-meterSheet-supported transition metal doped g-C 3 N 4 The synthesis method of the composite gas-sensitive material comprises the following steps: (1) Basic zinc carbonate and transition metal doped g-C 3 N 4 Grinding and mixing uniformly; (2) And (2) calcining the mixture obtained in the step (1) to obtain the composite gas-sensitive material. The method utilizes a precursor chemical synthesis method to dope g-C with transition metal with catalytic activity 3 N 4 The composite porous zinc oxide nano-sheet is compounded on a porous zinc oxide nano-sheet, and the gas-sensitive performance of zinc oxide is effectively improved by virtue of the synergistic effect between two porous two-dimensional semiconductor materials. The material can be used for gas-sensitive sensing detection of volatile organic pollutants (VOCs) and chlorobenzene gases, has good gas-sensitive response, is green, simple and convenient in material synthesis method, has good repeatability, and is easy to realize mass production and gas-sensitive detection application.
Description
Technical Field
The invention relates to g-C doped with transition metal loaded on porous zinc oxide nano-sheets for detecting VOCs (volatile organic chemicals) 3 N 4 A synthetic method of a composite gas sensitive material belongs to the field of inorganic nano material preparation.
Background
Indoor air quality researchers call that all volatile organic compounds sampled and analyzed indoors are VOCs, and the Volatile Organic Compounds (VOCs) are one of three types of indoor air pollutants which are seriously influenced. As people continue to grow indoors, the relationship between the indoor environment and people becomes more important. There are many methods for detecting VOCs, such as gas chromatography, infrared, SPR photodiode detection, gravimetric sensor, catalytic combustion sensor, photo ionization detector, etc., however, these methods have some disadvantages: analyzing the hysteresis of the detection is not favorable for online detection; the pretreatment and detection procedures of the sample are complicated. The gas-sensitive detection can just make up the weakness of the detection method, so the research on the synthesis method of the gas-sensitive material is particularly important.
The conductive gas sensor (gas sensor) detects the concentration change of a gas to be measured by detecting the change of the conductivity (resistance) before and after the reaction between a sensor sensitive element and a substance to be measured. As a common n-type semiconductor gas-sensitive material, zinc oxide has obvious gas-sensitive response in the detection of some VOCs gases and polychlorinated biphenyl pollutants, such as ethanol, acetone, chlorobenzene and the like. Nano zinc oxide materials of various morphologies, such as nanorods, nanosheets, nano flowers with multilevel structures, nano hollow structures, and the like, have been prepared by a liquid phase synthesis method. There are also many patent documents for zinc oxide materials used for preparing gas sensitive materials, such as: chinese patent document CN108190970A discloses a preparation method and application of a cobalt-doped zinc oxide gas-sensitive material, wherein polyvinylpyrrolidone (PVP), zinc acetate and cobalt nitrate hexahydrate are dissolved in 75ml of ethylene glycol, wherein the molar ratio of the polyvinylpyrrolidone with the molecular weight of 400000 to the zinc acetate hexahydrate is 0.025-0.233, and the cobalt-doped nano spherical zinc oxide gas-sensitive material is prepared. For another example: chinese patent document CN106541143A discloses a synthesis method of a porous zinc oxide nanosheet loaded high-dispersion nano precious metal composite gas-sensitive material. The method comprises the following steps: (1) Soaking basic zinc carbonate in an aqueous solution of noble metal ions, and stirring in the dark to obtain a reaction solution containing a precipitate; (2) And (2) carrying out centrifugal washing, drying and calcining on the precipitate in the reaction liquid obtained in the step (1) to obtain the composite gas-sensitive material. However, the nature of the zinc oxide material itself limits its sensitivity and speed of response to VOCs. The response value reflects the sensitivity of the response, and the response time and the recovery time reflect the response speed. The response time and recovery time are defined as: the time from zero response to 90% of the maximum response value and the time from the maximum response value to 10% of the maximum response value reflect the reaction speed after the gas is adsorbed on the surface of the gas sensitive material and the speed of the gas sensitive material returning to the initial state after the reaction is finished. On the basis of increasing the response value by multiple times, the response time and the recovery time are reduced to a certain extent, which means that the reaction speed and the recovery speed are obviously improved. For the transition metal directly doped zinc oxide material, the gas sensitivity performance of a few specific gases is obviously improved, but the gas sensitivity of a plurality of VOCs gases is difficult to be obviously improved. And different transition metals are directly doped with zinc oxide, and due to the limitation of lattice structures, synthesis conditions and methods are different, so that a simple and universal synthesis method aiming at different transition metals is difficult to assemble. For the composite gas sensitive material of zinc oxide supported noble metal, the cost of the noble metal is often higher, and the method has defects in the aspects of economy and environmental protection in practical application.
Transition metal (iron, copper, manganese, cobalt, nickel) doped graphite phase carbon nitride(g-C 3 N 4 ) The material has a two-dimensional porous structure, has excellent liquid-phase photocatalysis and organic gas heterogeneous catalysis activity, can effectively overcome the defects of a zinc oxide material by doping, and further improves the gas-sensitive performance of zinc oxide on various VOCs. Transition metal doped g-C 3 N 4 The triazine derivative has a certain s-triazine structure, the structure conforms to the principle of 4n +2 specified by the Huckel rule, and the triazine derivative has 6 delocalized electrons; while three N atoms and 3C atoms all adopt sp 2 All atoms are positioned on the same plane, and the porous two-dimensional planar semiconductor structure is completely regular. The transition metal elements of iron, copper, manganese, cobalt and nickel have certain catalytic capability respectively. Atoms of the transition metal element play a role in catalyzing the oxidation-reduction reaction of target VOCs gas at a higher temperature, the activation energy of the oxidation reaction is reduced, and g-C is doped in the loaded transition metal element 3 N 4 The porous zinc oxide nanosheet has better gas-sensitive performance and higher sensitivity. Doping transition metal element in g-C 3 N 4 On a plane structure, due to the g-C 3 N 4 Due to the limitation of a plane structure and a crystal structure, the transition metal is close to the uniform dispersion of atomic level, the number of active sites is more, the exposure is more sufficient, and the composite gas-sensitive material is more stable, so that the composite gas-sensitive material has better gas-sensitive response and sensitivity.
Transition metal (iron, copper, manganese, cobalt, nickel) doped g-C 3 N 4 The preparation of the material for photocatalysis and organic gas heterogeneous catalysis has been reported in the literature. For example: chinese patent document CN106540734A discloses a transition metal oxide composite CNB photocatalyst, which is formed by compounding CNB and a transition metal oxide, and has a good photocatalytic degradation effect on organic dyes, especially azo dyes or anthraquinone dyes, under ultraviolet light, and particularly after 1 hour of ultraviolet light irradiation, the degradation rate on methyl orange can reach more than 75%. Transition metal (iron, copper, manganese, cobalt, nickel) doped g-C 3 N 4 The material is used for heterogeneous catalysis of organic gas, but cannot be directly used for gas-sensitive detection of VOCs (volatile organic compounds) because the material has the characteristics ofThe detection method has the advantages that the detection method is catalytic but has no gas sensitivity, and the detection of the gas sensitivity of the VOCs can be realized only by using the synergistic effect of a composite material by using a traditional gas-sensitive material (such as zinc oxide) as a carrier.
However, the composite material of the porous zinc oxide nanosheet and the porous zinc oxide nanosheet is prepared by a chemical synthesis method and is effectively used for gas-sensitive detection of VOCs, and reports are not shown.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the g-C doped with transition metal loaded on the porous zinc oxide nano-sheet for detecting VOCs, which is simple, green and good in repeatability and can realize large-scale production 3 N 4 A method for synthesizing a composite gas-sensitive material.
The technical scheme of the invention is as follows:
porous zinc oxide nano-sheet loaded transition metal doped g-C for detecting VOCs 3 N 4 The synthesis method of the composite gas-sensitive material comprises the following steps:
(1) Basic zinc carbonate and transition metal doped g-C 3 N 4 Grinding and mixing uniformly;
(2) And (2) calcining the mixture obtained in the step (1) to obtain the composite gas-sensitive material.
According to the invention, the basic zinc carbonate in the step (1) is prepared by the following method: dissolving zinc acetate and urea in water, and reacting at 110-140 ℃ for 4-8h; centrifuging, washing and drying to obtain basic zinc carbonate;
further preferably, the reaction temperature is 120 ℃, and the reaction time is 5h;
further preferably, the molar ratio of the zinc acetate to the urea is 1; preferably, the molar ratio of the zinc acetate to the urea is 1;
further preferably, the drying condition is 60 ℃ for 12h.
According to the invention, the step (1) is preferably a transition metal doped g-C 3 N 4 The preparation method comprises the following steps: dissolving dicyandiamide and transition metal salt in water, uniformly mixing, and heating at 80 ℃ until the water is completely evaporated; drying, calcining under the protection of nitrogen,to obtain g-C doped with transition metal 3 N 4 。
More preferably, the transition metal is Fe, cu, mn, co, ni, and the transition metal salt is FeCl 2 、CuCl 2 、MnCl 2 、CoCl 2 、NiCl 2 、Fe(NO 3 ) 2 、Cu(NO 3 ) 2 、Mn(NO 3 ) 2 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 ；
Further preferably, the mass ratio of the dicyandiamide to the transition metal salt is 10-20;
further preferably, the drying condition is drying at 60 ℃ for 12h;
further preferably, the calcination temperature is 500-600 ℃ under the protection of nitrogen, and the reaction time is 3-6h; preferably, the calcining temperature is 550 ℃ and the reaction time is 4h.
According to the invention, in step (1), the basic zinc carbonate is doped with a transition metal in the form of g-C 3 N 4 The mass ratio of (A) to (B) is 3-6.
According to the invention, the calcination temperature in the step (2) is 350-450 ℃, and the calcination time is 2-4h.
Further preferably, the calcination condition is 400 ℃ for 2h.
According to the invention, the VOCs are chlorobenzene, toluene, formaldehyde, acetone or n-heptane.
The invention obtains a two-dimensional porous composite material by precursor calcination, and generates gases such as carbon dioxide and the like by calcination and basic zinc carbonate decomposition to generate g-C doped with transition metal and a zinc oxide porous structure 3 N 4 Can be uniformly and firmly attached to the surface of the zinc oxide; transition metal doped g-C 3 N 4 And the zinc oxide is a semiconductor with a porous sheet structure, so that the permeability of gas in gas-sensitive detection is improved, the response sensitivity is improved, and the two-dimensional plane structure is favorable for the conduction of electrons in the composite material to enhance a gas-sensitive response signal.
The invention has the beneficial effects that:
1. preparation of the inventionThe porous zinc oxide nano-sheet loads transition metal doped g-C 3 N 4 In the composite gas-sensitive material, g-C is doped due to transition metal 3 N 4 And zinc oxide are both porous sheet-like semiconductor, so that a two-dimensional sheet structure is basically reserved after calcination; the porous structure ensures the permeability of gas and improves the response sensitivity, and the two-dimensional plane structure is beneficial to the conduction of electrons in the composite material to enhance the gas-sensitive response signal. Active sites on the surface of the prepared material can be regulated and controlled by regulating and controlling the loaded mass ratio and the doping amount of the transition metal, so that the gas-sensitive performance is optimized.
2. The porous zinc oxide nano-sheet prepared by the invention loads transition metal doped g-C 3 N 4 In the composite gas-sensitive material, transition metal elements of iron, copper, manganese, cobalt and nickel have certain catalytic capacities respectively. Atoms of the transition metal elements play a role in catalyzing the oxidation-reduction reaction of the target VOCs gas at a higher temperature, and the activation energy of the oxidation reaction is reduced. g-C 3 N 4 Three N atoms and 3C atoms all adopt sp 2 The doped transition metal is close to the uniform dispersion of atomic level, the number of active sites is more, the exposure is more sufficient, and the doped transition metal is more stable, so that the composite gas-sensitive material has better gas-sensitive response and sensitivity.
3. The gas-sensitive detection response of the composite gas-sensitive material prepared by the method to VOCs and chlorobenzene gases is obviously superior to that of a pure nano zinc oxide material, and high-sensitive response to various gases is realized.
4. The preparation method is green, simple and convenient, has good repeatability, and is a process capable of being manufactured and applied in a large scale.
Drawings
FIG. 1 shows that the porous zinc oxide nanosheet prepared in example 1 is loaded with iron-doped g-C 3 N 4 And (3) a transmission electron microscope photo of the composite gas-sensitive material.
FIG. 2 shows copper-doped g-C loading of porous zinc oxide nanoplatelets prepared in example 2 3 N 4 And (3) a transmission electron microscope photo of the composite gas-sensitive material.
FIG. 3 shows that the porous zinc oxide nanoplatelets prepared in example 3 are loaded with manganese-doped g-C 3 N 4 Transmission electron micrograph of the composite gas sensitive material.
FIG. 4 shows that the porous zinc oxide nano-sheet prepared in example 4 supports cobalt-doped g-C 3 N 4 Transmission electron micrograph of the composite gas sensitive material.
FIG. 5 shows that the porous zinc oxide nano-sheet prepared in example 5 is loaded with nickel-doped g-C 3 N 4 And (3) a transmission electron microscope photo of the composite gas-sensitive material.
FIG. 6 shows that the porous zinc oxide nanosheet prepared in example 1 is loaded with iron-doped g-C 3 N 4 The X-ray diffraction pattern of the composite gas-sensitive material.
FIG. 7 shows copper-doped g-C loading of porous zinc oxide nanoplatelets prepared in example 2 3 N 4 X-ray diffraction pattern of the composite gas sensitive material.
FIG. 8 shows that the porous zinc oxide nanosheets prepared in example 3 are loaded with manganese doped g-C 3 N 4 The X-ray diffraction pattern of the composite gas-sensitive material.
FIG. 9 shows cobalt-doped g-C supported porous zinc oxide nanosheets prepared in example 4 3 N 4 The X-ray diffraction pattern of the composite gas-sensitive material.
FIG. 10 shows the porous zinc oxide nanosheet loaded iron-doped g-C prepared in example 1 3 N 4 Electronic energy spectrum of the composite gas sensitive material.
FIG. 11 is copper-doped g-C loading porous zinc oxide nanoplatelets prepared in example 2 3 N 4 Electronic energy spectrum of the composite gas sensitive material.
FIG. 12 shows that the porous zinc oxide nanosheets prepared in example 3 are loaded with manganese doped g-C 3 N 4 Electronic energy spectrum of the composite gas sensitive material.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Porous zinc oxide nanosheet load transition metal doped g-C 3 N 4 The synthesis method of the composite gas-sensitive material comprises the following steps:
(1) 15ml of a 0.2mol/L aqueous solution of zinc acetate was added to 15ml of a 0.4mol/L aqueous solution of urea, ultrasonically dispersed for 10min, and then the mixed solution was transferred to a stainless steel autoclave with a volume of 50mL lined with polytetrafluoroethylene and allowed to react in an oven at 120 ℃ for 5 hours. Naturally cooling to room temperature, centrifuging, washing with deionized water for 3 times, and drying in an oven at 60 deg.C for 12 hr to obtain basic zinc carbonate;
1g of dicyandiamide and 0.1g of FeCl 2 Adding into 15ml deionized water, stirring, mixing, heating at 80 deg.C until water content of the solution is evaporated to dryness, and drying in oven at 60 deg.C for 12 hr. Calcining the dried product for 4h at 550 ℃ under the protection of nitrogen atmosphere of a tube furnace, and naturally cooling to room temperature to obtain the iron-doped g-C 3 N 4 ；
(2) The basic zinc carbonate and the iron-doped g-C obtained in the step (1) 3 N 4 And (2) mixing according to the mass ratio of 3.
FIG. 1 shows that the porous zinc oxide nanosheet prepared in this example is loaded with iron-doped g-C 3 N 4 As can be seen from FIG. 1, the TEM image of the composite gas-sensitive material shows that the material composition is realized on the surface of the porous zinc oxide nanosheet.
FIG. 6 shows that the porous zinc oxide nanosheet prepared in this example is loaded with iron-doped g-C 3 N 4 As can be seen from FIG. 6, the X-ray diffraction pattern of the composite gas-sensitive material showed g-C in addition to the diffraction peak of wurtzite zinc oxide (corresponding to JCPDS No.36-1451, standard card) 3 N 4 Diffraction Peak (corresponding to g-C) 3 N 4 (002) Crystal face) without other hetero peaks.
FIG. 10 shows the porous zinc oxide nanosheet loaded iron-doped g-C prepared in this example 3 N 4 Electronic energy spectrum and visible material of composite gas-sensitive materialThe surface layer of the material has iron element, so the composite material is zinc oxide and g-C doped with iron 3 N 4 The composite material of (1) has no other matter structure.
Example 2
As described in example 1, except that 0.1g of Cu (NO) was used in step (2) 3 ) 2 In place of 0.1g FeCl 2 。
FIG. 2 shows copper-doped g-C loading of porous zinc oxide nanoplatelets prepared in this example 3 N 4 As can be seen from FIG. 2, the TEM image of the composite gas-sensitive material shows that the material composition is realized on the surface of the porous zinc oxide nanosheet.
FIG. 7 shows the copper-doped g-C loading of porous zinc oxide nanoplatelets prepared in this example 3 N 4 As can be seen from FIG. 7, the X-ray diffraction pattern of the composite gas-sensitive material showed g-C in addition to the diffraction peak of wurtzite zinc oxide (corresponding to JCPDS No.36-1451, standard card) 3 N 4 Diffraction Peak (corresponding to g-C) 3 N 4 (002) Crystal face) without other hetero peaks.
FIG. 11 shows copper-doped g-C loading of porous zinc oxide nanoplatelets prepared in this example 3 N 4 The electron energy spectrum of the composite gas-sensitive material shows that copper element exists on the surface layer of the material, so that the composite material is g-C doped with zinc oxide and copper 3 N 4 The composite material of (1) has no other matter structure.
Example 3
Except that 0.06g of MnCl was used in step (2) as described in example 1 2 In place of 0.1g FeCl 2 。
FIG. 3 shows that the porous zinc oxide nanosheet prepared in this example is loaded with manganese-doped g-C 3 N 4 As can be seen from FIG. 3, the TEM image of the composite gas-sensitive material shows that the material composition is realized on the surface of the porous zinc oxide nanosheet.
FIG. 8 shows that the porous zinc oxide nanosheets prepared in this example are loaded with manganese-doped g-C 3 N 4 As can be seen from FIG. 8, the X-ray diffraction pattern of the composite gas sensitive material showed other diffraction peaks (corresponding to JCPDS No.36-1451, standard card) of wurtzite zinc oxideg-C 3 N 4 Diffraction Peak (corresponding to g-C) 3 N 4 (002) Crystal face) without other hetero peaks.
FIG. 12 shows that the porous zinc oxide nanosheet prepared in this example is loaded with manganese doped g-C 3 N 4 The electronic energy spectrum of the composite gas-sensitive material shows that manganese exists on the surface layer of the material, so that the composite material is g-C doped with zinc oxide and manganese 3 N 4 The composite material of (1) has no other matter structure.
Example 4
As described in example 1, except that 0.1g of CoCl was used in step (2) 2 In place of 0.1g FeCl 2 In step (3), basic zinc carbonate and cobalt-doped g-C 3 N 4 Mixing according to a mass ratio of 6.
FIG. 4 shows the cobalt-doped g-C supported by porous zinc oxide nanoplatelets prepared in this example 3 N 4 As can be seen from FIG. 4, the TEM image of the composite gas-sensitive material shows that the material composition is realized on the surface of the porous zinc oxide nanosheet.
FIG. 9 shows that the porous zinc oxide nanosheets prepared in this example were loaded with cobalt-doped g-C 3 N 4 As can be seen from FIG. 9, the X-ray diffraction pattern of the composite gas-sensitive material showed relatively weak g-C except for the diffraction peak of wurtzite zinc oxide (corresponding to JCPDS No.36-1451, standard card) 3 N 4 Diffraction Peak (corresponding to g-C) 3 N 4 (002) Crystal face) without other hetero peaks. The composite material is g-C doped with zinc oxide and cobalt 3 N 4 The composite material of (1) has no other matter structure.
Example 5
As described in example 1, except that 0.05g of Ni (NO) was used in step (2) 3 ) 2 In place of 0.1g FeCl 2 Basic zinc carbonate and nickel doped g-C in step (3) 3 N 4 And (3) mixing according to the mass ratio of 5.
FIG. 5 shows that the porous zinc oxide nano-sheet prepared in this example is loaded with nickel-doped g-C 3 N 4 As can be seen from FIG. 5, the TEM image of the composite gas-sensitive material shows that the material composition is realized on the surface of the porous zinc oxide nanosheet.
Comparative example 1
A porous zinc oxide nano-sheet is prepared by the following steps:
(1) 15ml of a 0.2mol/L aqueous solution of zinc acetate was added to 15ml of a 0.4mol/L aqueous solution of urea, ultrasonically dispersed for 10min, and then the mixed solution was transferred to a stainless steel autoclave with a volume of 50mL lined with polytetrafluoroethylene and allowed to react in an oven at 120 ℃ for 5 hours. Naturally cooling to room temperature, centrifuging, washing with deionized water for 3 times, and drying in an oven at 60 deg.C for 12 hr to obtain basic zinc carbonate;
(2) And (2) calcining the basic zinc carbonate obtained in the step (1) in a muffle furnace at 400 ℃ for 2 hours to obtain porous zinc oxide nano-sheets.
Comparative example 2
Porous zinc oxide nano-sheet loaded magnesium-doped g-C 3 N 4 The synthesis method of the composite gas-sensitive material comprises the following steps:
(1) 15ml of a 0.2mol/L aqueous solution of zinc acetate was added to 15ml of a 0.4mol/L aqueous solution of urea, ultrasonically dispersed for 10min, and then the mixed solution was transferred to a stainless steel autoclave with a volume of 50mL lined with polytetrafluoroethylene and allowed to react in an oven at 120 ℃ for 5 hours. Naturally cooling to room temperature, centrifuging, washing with deionized water for 3 times, and drying in an oven at 60 deg.C for 12 hr to obtain basic zinc carbonate;
(2) 1g of dicyandiamide and 0.1g of MgCl 2 Adding into 15ml deionized water, stirring, mixing, heating at 80 deg.C until water content of the solution is evaporated to dryness, and drying in oven at 60 deg.C for 12 hr. Calcining the dried product for 4h at 550 ℃ under the protection of nitrogen atmosphere of a tube furnace, and naturally cooling to room temperature to obtain magnesium-doped g-C 3 N 4 ；
(3) Basic zinc carbonate and magnesium doped g-C obtained in steps (1) and (2) 3 N 4 Mixing according to the mass ratio of 3 3 N 4 A composite gas sensitive material.
Test example 1
The gas-sensitive materials prepared in examples 1 to 5 and comparative examples 1 and 2 were subjected to gas-sensitive performance tests, the test methods were as follows:
1. the instrument used for testing is a WS-30A gas-sensitive tester produced by Zhengzhou weisheng electronic technology limited, and the gas-sensitive element is a indirectly-heated sintered element manufactured according to the traditional method.
2. 0.3g of the synthesized gas-sensitive material sample is added into a mortar, a small amount of ethanol is dropped into the mortar until the mixture is ground uniformly into paste, and the paste is uniformly coated on the periphery of an alumina ceramic tube with gold electrodes at two ends by a fine brush.
3. After the sample is completely dried on the ceramic tube, 4 platinum wire lead connectors are welded on the element base, then the heating wire penetrates through the ceramic tube, two ends of the heating wire are also welded on the element base to manufacture the gas sensitive element, and then the element is placed on an aging table to be aged for 5-7 days at 440 ℃.
4. After the gas-phase object to be tested is injected into the test bin, the sensitive characteristic of the gas sensitive element is reflected by recording the voltage on a load resistor connected with the gas sensitive element in series. The sensitivity response value (S) of the gas sensor is defined as S = Ra/Rg, and Ra and Rg are resistance values of the gas sensor in air and gas to be measured, respectively.
The gas-sensitive performance test results of the gas-sensitive materials prepared in examples 1 to 5 and comparative examples 1 and 2 are shown in table 1:
TABLE 1
Comprehensively analyzing, and loading the prepared porous zinc oxide nano-sheet with g-C doped with transition metal 3 N 4 The gas-sensitive detection response values of the composite gas-sensitive material (for example, examples 1 to 5) on VOCs and chlorobenzene gases are obviously superior to those of pure nano zinc oxide and zinc oxide loaded magnesium-doped g-C 3 N 4 And high for various kinds of gases are achieved (for example, comparative examples 1, 2)Sensitive response, response and recovery time are also faster.
Claims (2)
1. Porous zinc oxide nanosheet load transition metal doped g-C for detecting chlorobenzene 3 N 4 The synthesis method of the composite gas-sensitive material comprises the following steps:
(1) Adding 15mL of 0.2mol/L zinc acetate aqueous solution into 15mL of 0.4mol/L urea aqueous solution, carrying out ultrasonic dispersion for 10min, transferring the mixed solution into a stainless steel autoclave with the volume of 50mL and a polytetrafluoroethylene lining, and reacting the stainless steel autoclave in an oven at the temperature of 120 ℃ for 5h; naturally cooling to room temperature, centrifuging, washing with deionized water for 3 times, and drying in an oven at 60 deg.C for 12 hr to obtain basic zinc carbonate;
1g of dicyandiamide and 0.1g of FeCl 2 Adding into 15ml deionized water, stirring, mixing, heating at 80 deg.C until water content of the solution is evaporated to dryness, and drying in oven at 60 deg.C for 12 hr; calcining the dried product for 4h at 550 ℃ under the protection of nitrogen atmosphere of a tube furnace, and naturally cooling to room temperature to obtain the iron-doped g-C 3 N 4 ；
(2) The basic zinc carbonate and the iron-doped g-C obtained in the step (1) 3 N 4 And (2) mixing according to the mass ratio of 3.
2. Porous zinc oxide nano-sheet loaded transition metal doped g-C for detecting methylbenzene 3 N 4 The synthesis method of the composite gas-sensitive material comprises the following steps:
(1) Adding 15mL of 0.2mol/L zinc acetate aqueous solution into 15mL of 0.4mol/L urea aqueous solution, carrying out ultrasonic dispersion for 10min, transferring the mixed solution into a stainless steel autoclave with the volume of 50mL and the inner lining of polytetrafluoroethylene, and reacting the mixed solution in an oven at 120 ℃ for 5h; naturally cooling to room temperature, centrifuging, washing with deionized water for 3 times, and drying in an oven at 60 deg.C for 12 hr to obtain basic zinc carbonate;
1g of dicyandiamide and 0.1g of Cu (NO) 3 ) 2 Or 0.06g MnCl 2 Adding into 15ml deionized water, stirring, mixing, heating at 80 deg.C until water content of the solution is evaporated to dryness, and drying in oven at 60 deg.C for 12 hr; calcining the dried product for 4 hours at 550 ℃ under the protection of nitrogen atmosphere of a tube furnace, and naturally cooling to room temperature to obtain copper or manganese doped g-C 3 N 4 ；
(2) Basic zinc carbonate and copper or manganese doped g-C obtained in step (1) 3 N 4 And (2) mixing according to the mass ratio of 3.
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