CN114452998A - Preparation method and application of multi-walled carbon nanotube and graphitized carbon nitride composite material - Google Patents
Preparation method and application of multi-walled carbon nanotube and graphitized carbon nitride composite material Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
The invention belongs to the field of new materials, and provides a preparation method and application of a multi-walled carbon nanotube and graphitized carbon nitride composite material. The CNN composite material is prepared from graphitized carbon nitride g-C3N4And the carboxylated carbon nano-tube CNTs are calcined in an inert atmosphere. In the calcining process, a soft template is added as a pore-forming agent, so that the specific surface area of the composite material is improved. The composite CNN material prepared by the invention is used for photocatalysis of CO by using infrared light2The conversion reaction for preparing CO shows excellent activity. The composite material is different from other photocatalytic materials and can be catalyzed by using spectral energy below 800 nm. The CNN material greatly expands the range of the semiconductor material capable of absorbing and utilizing the spectrum, and improves the utilization rate of solar energy. Simultaneously can effectively remove greenhouse gas CO2And is converted into CO with higher utilization value.
Description
Technical Field
The invention belongs to the field of new materials, and relates to a novel graphitized carbon nitride composite material (CNN). Firstly, the carboxylated multi-walled carbon nano-tube is dispersed by ultrasonic, and then is added into a solution containing dicyandiamide and ammonium chloride to be thoroughly and uniformly mixed. After the moisture is evaporated to dryness, the mixture is calcined in an inert gas atmosphere to obtain the composite material CNN of the carbon nano tube and the carbon nitride, and the composite material can effectively utilize solar energy in an infrared light area. The invention also relates to the application of the composite material in the field of photocatalytic carbon dioxide reduction.
Background
The continuous consumption of fossil energy not only brings energy crisis, combustionCO released during burning2The resulting greenhouse effect also seriously affects the environment in which humans live. Therefore, how to develop and utilize clean and renewable energy sources becomes the most concerned problem. Photocatalytic CO2The solar energy can be utilized to convert greenhouse gases into formic acid, carbon monoxide, methane and the like which have value for human beings. How to utilize solar energy for CO2Reduction is a hot problem. A plurality of researches prove that certain semiconductor materials can effectively absorb light energy to catalyze CO2And (4) transformation. However, there are still many areas of interest and improvement in this area of research.
The light energy as a renewable energy source with abundant reserves has the advantages of simple and convenient acquisition, high energy, wide coverage range and the like. Solar radiation can reach 173,000 TW/s, which is equivalent to the energy provided by burning 500 million tons of coal. In the current photocatalytic reaction, the solar energy absorbed by the photocatalyst is determined by the band gap of the photocatalyst. In general, the band gap of the semiconductor is satisfied to be able to catalyze CO2The size is determined in the case of transformation. The size of the band gap in turn determines the spectral range that the semiconductor catalyst can utilize. So that the most widely used g-C3N4For example, the band gap is about 2.7eV, and only the ultraviolet region in the solar spectrum is often used. The proportion of ultraviolet light in the sunlight radiated to the earth is only about 3 percent, and the rest is visible light and infrared light. How to expand the available solar spectrum as much as possible while ensuring the catalytic activity of the catalyst is the most interesting issue.
Cheng et al (adv. Mater.2015,27, 4572-4577) developed an amorphous C with an in-plane highly disordered structure3N4Due to the existence of the disordered structure, the photoproduction excitons can be quickly separated, and the service life of the photoproduction electrons is greatly prolonged. In addition, the structure can also reduce C3N4The band gap expands the absorption spectrum of the solar cell and improves the utilization rate of solar energy. Under the irradiation of a 300wXe lamp, the catalytic material shows marked photocatalytic hydrogen production activity; li et al (adv. Mater.2021,33,2102690) prepared three-dimensional ordered macroporous N-doped carbon (NC) -loaded CdS quantum by in-situ conversion methodPoint (3DOM CdSQD/NC) photocatalyst for photocatalytic CO2And (3) RR. The catalyst can effectively utilize solar energy in ultraviolet and partial visible light regions, and exhibits an apparent quantum efficiency of 2.9% at 450 nm. Under the condition of not adding any sacrificial agent, the generation rate of CO reaches 5210umol/g/h to the maximum; xie et al (Joule,2018,2, 1004-1016) prepared WO3 materials with different numbers of defects by hydrogen reduction, with the number of defects increasing WO33Gradually darkens in color. The catalytic material has ultraviolet absorption in an infrared light region due to the intermediate band gap caused by defects, and infrared light with lower photon energy and higher quantity can be utilized. As mentioned above, although there are many semiconductor photocatalysts today, most catalysts can only utilize ultraviolet and some visible light. In the solar spectrum, the energy in the infrared region accounts for more than 55%, and how to utilize the energy becomes an important problem for efficiently utilizing the solar energy. Although there are some examples of catalysis using infrared light, the amount is still far from sufficient, and the effect is still to be improved.
In conclusion, the prepared photocatalyst can efficiently utilize the energy of the solar infrared region for photocatalysis to remove the greenhouse gas CO2Catalytic conversion to CO products that are of higher utility to humans is an important issue. The invention utilizes carboxylated multi-walled carbon nanotubes with narrow band gap and common photocatalytic semiconductor g-C3N4And (6) compounding. Ammonium chloride was used as a pore former and soft template. During the heating and calcining process, the ammonium chloride is decomposed and escaped, so that the composite material is more loose and porous and has larger specific surface area, and more reactive active sites are exposed. Using the surface functional groups of CNTs with g-C3N4Chemical bonding is formed between the two, so that the photo-generated charges can be transferred and separated more quickly, and the reaction is facilitated. By means of the unique energy band structure of the CNTs, the composite material CNN can effectively utilize the energy in the infrared light region to carry out photocatalysis on CO2And (4) transformation. Under the illumination of 600-750nm and 850-1100nm, the CNN material can convert CO into CO2Is converted into CO. And g-C3N4But can only utilize energy in the ultraviolet and partially visible regions. CNN material for catalyzing CO in infrared light region2The highest efficiency of converting into CO can reach 1.7umol/g/h, the material can greatly expand the spectrum range of available areas, and the utilization rate of solar energy is improved.
Disclosure of Invention
The invention aims to prepare a catalyst capable of exposing more active sites by utilizing the soft template action of ammonium chloride. Simultaneously utilizes functional groups on the surface of the carboxylated carbon nano tube to react the CNTs with the g-C3N4The coupling is performed. Due to the unique photoelectric characteristics of the CNTs, the obtained CNN composite sample has the characteristic of being capable of absorbing and utilizing photon energy in an infrared region. The invention can greatly expand the utilization rate of the photocatalyst to solar energy.
The technical scheme of the invention is as follows:
a multi-wall carbon nano-tube and graphitized carbon nitride composite material, wherein the CNN composite material is prepared from graphitized carbon nitride g-C3N4And the carboxylated carbon nano-tube CNTs are calcined in an inert atmosphere. In the calcining process, a soft template is added as a pore-forming agent, so that the specific surface area of the composite material is improved. Carboxyl groups and g-C on the surface of CNTs3N4And bonding the two. The composite material can effectively utilize the energy of the infrared region of sunlight.
The composite sample still retains g-C through XRD test3N4Characteristic peaks of (A), indicating that the addition of CNTs does not alter g-C3N4The crystal structure of (1).
A preparation method of a multi-walled carbon nanotube and graphitized carbon nitride composite material comprises the following steps:
step (1): fully mixing the precursors:
firstly, dicyandiamide, ammonium chloride and carbon nano tubes are mixed according to the mass ratio of 10: 10: 1, mixing and dispersing in deionized water, and performing ultrasonic treatment to uniformly disperse to obtain a mixed solution; wherein the mass concentration of the dicyandiamide is 3 g/L;
stirring and heating the mixed solution obtained in the step one in a water bath kettle at the temperature of 60-80 ℃, evaporating the water in the mixed solution to dryness, and obtaining a gray black solid coated with recrystallized dicyandiamide and ammonium chloride on the surface of the carbon nano tube;
ball-milling the obtained grey-black solid into uniform grey-black powder;
step (2): preparation of CNN composite material:
and (2) transferring the uniformly mixed gray black powder obtained in the step (1) to a tubular furnace, introducing inert gas, evacuating for 1h, heating at the speed of 2-5 ℃/min, calcining for 1-2h at 550 ℃, cooling to room temperature, and grinding the black solid obtained by calcining to obtain the composite material.
The composite material prepared by the preparation method is used for photocatalysis of CO2Application in conversion by photocatalytic CO using CNN composite material2The test procedure for conversion was carried out and the CO product was detected by gas chromatography, as follows:
firstly, dispersing a composite material in deionized water, wherein the concentration of the composite material in the deionized water is 0.1 g/L; after ultrasonic dispersion is uniform, transferring the mixture to a stainless steel reaction kettle, and introducing CO after packaging2Ventilating for 1-2h to completely exhaust other gases in the reaction kettle;
illuminating the reaction kettle by using a 300WXe lamp, wherein a 600nm optical filter or an 800nm optical filter is used during illumination to ensure that the wavelengths of light emitted into the reaction kettle are respectively 600 plus 750nm and 800 plus 1100nm, and the temperature of the reaction kettle is kept constant by condensed water at 25 ℃;
thirdly, after reacting for a certain time, injecting the gas in the reaction kettle into the gas chromatography by using an injector for detection.
The invention has the beneficial effects that: the composite CNN material prepared by the invention can be used for photocatalysis of CO by using infrared light2The conversion reaction for preparing CO shows excellent activity. The composite material is different from other photocatalytic materials and can be catalyzed by using spectral energy below 800 nm. The CNN material greatly expands the range of the semiconductor material capable of absorbing and utilizing the spectrum, and improves the utilization rate of solar energy. Simultaneously can effectively remove greenhouse gas CO2And is converted into CO with higher utilization value.
Drawings
Fig. 1 is an XRD pattern of CNN composite. It can be seen that the composite CNN still retains g-C3N4Characteristic peak of (2). Indicating that the addition of CNTs does notChanging g-C3N4The crystal structure of (1).
FIG. 2(a) shows g-C3N4N of (A)2The isothermal adsorption-desorption curve shows that the specific surface area of the composite sample is obviously improved.
FIG. 2(b) is N of CNN composite2An isothermal adsorption and desorption curve shows that the specific surface area of the composite sample is obviously improved.
FIG. 3 shows the photocatalytic performance of CNN composite material in different wavelength ranges, from which it can be seen that the CO yield is significantly higher than that of pure C when the composite material CNN is used3N4The yield of (2). Notably, g-C when irradiated using infrared wavelengths3N4The material can not catalyze CO2But the CNN composite material can be converted photo-catalytically using infrared wavelengths.
Detailed Description
The present invention is further illustrated by the following specific examples. The material to which the present invention relates is not limited to the expressions in the following examples.
Example 1
Dispersing 100mg of CNTs, 1g of dicyandiamide and 1g of ammonium chloride in 30mL of deionized water, performing ultrasonic treatment to uniformly disperse the CNTs, 1g of dicyandiamide and 1g of ammonium chloride, and evaporating the solution to dryness in a water bath kettle at 60-80 ℃ to obtain gray black powder for later use;
and (3) putting the gray black powder into a ball milling tank for ball milling, and performing ball milling for 30min by using a ball mill with the oscillation frequency of 50Hz to ensure that uniformly dispersed powder is obtained. Then transferring the powder into a tube furnace, introducing inert gas, and heating to 550 ℃ for calcination. Cooling to room temperature and grinding to obtain the CNN composite material;
the mixture was heated to 550 ℃ at 2 ℃/min in a tube furnace under an inert atmosphere, thermostatted for 2 hours and then lowered to room temperature at the same rate.
Example 2
The procedure was as in example 1. Except that the carboxylated carbon nanotubes were not added to the solution of dicyandiamide and ammonium chloride. Otherwise, all the operating steps and the amounts are the same. XRD and specific surface area of the prepared sample were measured as above fig. 1 and 2.
Example 3
The procedure was as in example 1. Except that dicyandiamide was not added to the solution of CNTs and ammonium chloride. Obtaining g-C free at the same preparation temperature3N4Samples, except for the above, all the procedures and amounts were the same. The XRD of the prepared N-doped CNTs sample is as above in fig. 1.
Example 4
And (3) dispersing 10mg of the composite material in 100mL of deionized water, uniformly dispersing by ultrasonic, transferring to a stainless steel reaction kettle, introducing CO2 after packaging is finished, and completely exhausting other gases in the reaction kettle after introducing the CO2 for 1-2 h. The reactor is illuminated by a 300W Xe lamp, a 600nm filter is used during illumination to ensure that the wavelength of light emitted into the reaction kettle is 600-750nm, and the temperature of the reactor is kept constant by 25 ℃ condensed water. After reacting for 2h, the gas in the 1.5mL reactor was injected into the gas chromatograph for detection.
Example 5
Dispersing the composite material 10 in 100mL of deionized water, transferring the mixture to a stainless steel reaction kettle after the ultrasonic dispersion is uniform, and introducing CO after the encapsulation is finished2And ventilating for 1-2h to completely exhaust other gases in the reaction kettle. The reactor is illuminated by a 300W Xe lamp, an 800nm filter is used during illumination to ensure that the wavelength of light emitted into the reaction kettle is 800-1100nm, and the temperature of the reactor is kept constant by 25 ℃ condensed water. After reacting for 2h, the gas in the 1.5mL reactor was injected into the gas chromatograph for detection.
The yield ratio of example 3 and example 4 is shown in fig. 3.
The CNN composite material breaks through the defects of the traditional semiconductor as the photocatalyst, and can fully utilize the infrared light area energy which cannot be utilized by the traditional semiconductor catalyst. Under the condition of incidence of infrared light, the greenhouse gas CO can be emitted2Effectively converted into CO, greatly expands the light absorption range of the semiconductor catalyst and improves the utilization rate of solar energy. Catalysis of CO under infrared light irradiation2The yield of the transformation is shown in FIG. 3. The CNN composite material becomes a novel photocatalysisThe material greatly improves the utilization rate of solar energy and shows good application prospect.
Claims (3)
1. A preparation method of a multi-walled carbon nanotube and graphitized carbon nitride composite material is characterized by comprising the following steps:
step (1): fully mixing the precursors:
firstly, dicyandiamide, ammonium chloride and carbon nano tubes are mixed according to the mass ratio of 10: 10: 1, mixing and dispersing in deionized water, and performing ultrasonic treatment to uniformly disperse to obtain a mixed solution; wherein the mass concentration of the dicyandiamide is 3 g/L;
stirring and heating the mixed solution obtained in the step one in a water bath kettle at the temperature of 60-80 ℃, evaporating the water in the mixed solution to dryness, and obtaining a gray black solid coated with recrystallized dicyandiamide and ammonium chloride on the surface of the carbon nano tube;
ball-milling the obtained grey-black solid into uniform grey-black powder;
step (2): preparation of CNN composite material:
and (2) transferring the uniformly mixed gray black powder obtained in the step (1) to a tubular furnace, introducing inert gas, evacuating for 1h, calcining for 1-2h at 550 ℃, cooling to room temperature, and grinding the black solid obtained by calcining to obtain the composite material.
2. The production method according to claim 1, wherein the temperature increase rate during the calcination in the step (2) is 2 to 5 ℃/min.
3. Use of the composite material obtained by the preparation method of claim 1 or 2 in photocatalysis of CO2Use in conversion, characterised in that CNN composite materials are used, according to which CO is photocatalytic2The test procedure for conversion was carried out and the CO product was detected by gas chromatography, as follows:
firstly, dispersing a composite material in deionized water, wherein the concentration of the composite material in the deionized water is 0.1 g/L; after ultrasonic dispersion is uniform, transferring the mixture to a stainless steel reaction kettle, and introducing CO after packaging2And the reaction kettle is completely emptied by introducing air for 1-2hOther gases;
illuminating the reaction kettle by using a 300WXe lamp, wherein a 600nm optical filter or an 800nm optical filter is used during illumination to ensure that the wavelengths of light emitted into the reaction kettle are respectively 600 plus 750nm and 800 plus 1100nm, and the temperature of the reaction kettle is kept constant by condensed water at 25 ℃;
thirdly, after reacting for a certain time, injecting the gas in the reaction kettle into the gas chromatography by using an injector for detection.
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