CN114717690A - Preparation method and application of biomass carbon-based material - Google Patents

Preparation method and application of biomass carbon-based material Download PDF

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CN114717690A
CN114717690A CN202210337943.8A CN202210337943A CN114717690A CN 114717690 A CN114717690 A CN 114717690A CN 202210337943 A CN202210337943 A CN 202210337943A CN 114717690 A CN114717690 A CN 114717690A
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temperature
treatment
nitrogen
porous carbon
biomass
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袁文静
周晨亮
石绍渊
万印华
胡康
鞠培海
张宝之
章星宇
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Ganjiang Innovation Academy of CAS
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention provides a preparation method and application of a biomass carbon-based material. The preparation method comprises the following steps: (1) pretreating the imperata cylindrica to obtain a biomass carbon precursor, and calcining the biomass carbon precursor after standing to obtain nitrogen-doped porous carbon fiber; (2) placing the nitrogen-doped porous carbon fiber obtained in the step (1) into a Pd-containing material2+And sequentially performing adsorption, suction filtration, drying and reduction treatment in the ionic solution to obtain the biomass carbon-based material. The biomass carbon-based material is prepared by taking the biomass imperata cone inflorescence as a precursor, is composed of porous carbon with a nitrogen-rich structure and Pd nano-particles, and sequentially acts on the adsorption and degradation of formaldehyde so as to realize the adsorption and degradation of formaldehydeThereby realizing the aim of purifying indoor formaldehyde pollution at room temperature.

Description

Preparation method and application of biomass carbon-based material
Technical Field
The invention relates to the field of carbon materials for purifying formaldehyde, and relates to a preparation method and application of a biomass carbon-based material.
Background
Formaldehyde, one of the volatile organic compounds, is widely recognized as a toxic and harmful indoor air pollutant, which is released from furniture and building materials, and causes negative effects on human health, such as chronic bronchitis, eye irritation, and even cancer induction. To improve indoor air quality, it is very urgent to effectively remove indoor formaldehyde pollutants. At present, the indoor formaldehyde pollutants are mainly removed by an adsorption method, a catalytic oxidation method, a plasma oxidation method and the like. Among these promising technologies, adsorption of porous carbon materials is an old technology but contributes to the enhancement of the ability to catalyze the oxidation of formaldehyde at room temperature, and therefore a high-efficiency room-temperature catalyst should generally have a strong adsorption ability. Theoretically, the formaldehyde molecule is a polar molecule, contains carbonyl oxygen atoms, and lone-pair electrons on the carbonyl oxygen atoms interact with Lewis acid sites to easily form adsorbed formaldehyde. At the same time, the carbonyl carbon atoms in the formaldehyde molecule tilt the electron cloud towards the oxygen atoms. Thus, the carbonyl carbon atom is electrophilic, usually interacting with lewis base sites. Therefore, it is reasonable and feasible to construct a novel Lewis acid-base pair structure on the surface of the adsorbent framework so as to improve the adsorption capacity to formaldehyde. Researches show that by constructing a nitrogen-rich structure, the surface of neutral porous carbon can be effectively polarized, and the adsorption performance of the neutral porous carbon is further improved.
Biomass, including plant straws, fruit peels and even animal wastes, is a renewable resource and is also a double-edged sword. If used properly, can benefit mankind, but if discarded at will, can pollute the surrounding environment.
CN 103433001A discloses a preparation method of a biomass arsenic adsorption material, which is characterized in that peanut vines containing protein are modified, and the adsorption quantity of pentavalent arsenic ions is increased by utilizing the chelation and adsorption effects of saccharomycetes and cyclodextrin on the pentavalent arsenic ions. The adsorption performance of the material is improved by using biomass, but the adsorption force of the adsorption material prepared by the method on formaldehyde is weaker, and the adsorption requirement of the formaldehyde cannot be met.
CN 109126730A discloses a biomass porous adsorption material and a preparation method and application thereof, wherein irradiation can effectively destroy the fiber internal structure of a raw material biomass material, and the biomass adsorption material introduces amino groups on a biomass molecule main chain by one step, so that the functionalization of the biomass porous material is realized, the specific surface area of the material is increased, and the adsorption force of the material is improved. The method adopts a method of irradiating biomass materials in air, and light pollution is generated. In addition, the biomass material after irradiation treatment is treated, the treatment process comprises freezing, normal-temperature stirring, filtering, water washing and the like, the preparation process is complex, the production cost is high, and the method is not suitable for large-scale production.
Therefore, how to prepare the biomass carbon-based material which is low in cost and can be produced on a large scale and can purify formaldehyde efficiently is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of a biomass carbon-based material, which have the effects of efficiently purifying indoor formaldehyde pollution and simultaneously have the economical efficiency of preparation cost and the feasibility of large-scale generation.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of biomass carbon-based material, which comprises the following steps:
(1) pretreating the imperata cylindrica to obtain a biomass carbon precursor, and calcining the obtained biomass carbon precursor to obtain nitrogen-doped porous carbon fibers;
(2) subjecting the nitrogen-doped porous carbon fiber obtained in the step (1) toVitamin is placed in a place containing pd2+And sequentially performing adsorption, suction filtration, drying treatment and reduction treatment in the ionic solution to obtain the biomass carbon-based material.
The biomass carbon-based material is prepared by taking the biomass imperata cone inflorescence as a precursor, and is used as a catalyst material, the catalyst is composed of porous carbon with a nitrogen-rich structure and Pd nano particles, and the catalyst is sequentially acted on the adsorption and degradation of HCHO, so that the aim of purifying indoor HCHO pollution at room temperature is fulfilled. The cogongrass is a common biomass, is a perennial herbaceous plant, and meets the requirements of low cost, environmental protection and large-scale production. Especially imperata cylindrica derived carbons, usually have a high specific surface area and rich porosity, enabling better exposure of adsorption sites, which is crucial for adsorbing formaldehyde. The method takes the imperata cone inflorescence as a precursor, and converts the imperata cone inflorescence into a valuable carbon-based catalyst from the aspect of changing waste into valuable.
Firstly, cleaning collected biomass imperata cone inflorescences, and then carrying out hydrothermal treatment on the biomass imperata cone inflorescences to obtain a precursor; then, placing the precursor in a tubular furnace with ammonia atmosphere for calcining to obtain nitrogen-doped porous carbon fibers; and finally, loading Pd nano particles on the surface of the prepared nitrogen-doped porous carbon fiber to obtain the biomass carbon-based material. The preparation method is simple, the raw materials are cheap and easy to obtain, and the large-scale production potential is large.
As a preferable technical scheme of the invention, the pretreatment in the step (1) comprises the steps of washing the anthodium arundinaceum panicle by using deionized water, and carrying out hydrothermal reaction on the washed anthodium arundinaceum panicle.
Preferably, the hydrothermal reaction is carried out using a polytetrafluoroethylene-lined reaction vessel.
Preferably, the volume of the reaction vessel in the hydrothermal reaction is 20 to 150mL, wherein the volume may be 20mL, 30mL, 40mL, 50mL, 60mL, 70mL, 80mL, 90mL, 100mL, 110mL, 120mL, 130mL, 140mL, 150mL, or the like, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the hydrothermal reaction is 120 to 200 ℃, wherein the temperature may be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the hydrothermal reaction time is 5 to 20 hours, wherein the time can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours, but the hydrothermal reaction time is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a preferred embodiment of the present invention, the biomass carbon precursor in step (1) is dried at room temperature for 2 to 8 days, wherein the number of days may be 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, etc., but the number is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the temperature of the room temperature is 5 to 35 ℃, wherein the temperature can be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical scheme of the invention, the calcination treatment in the step (1) comprises heating calcination treatment, heat preservation calcination treatment and cooling calcination treatment which are sequentially carried out.
Preferably, the temperature rise rate of the temperature rise calcination treatment is 2 to 15 ℃/min, wherein the temperature rise rate can be 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min or 15 ℃/min, and the like, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the heat-preserving calcination treatment is 600 to 1000 ℃, wherein the temperature can be 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time for the heat-preservation calcination treatment is 0.5 to 5 hours, wherein the time can be 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the cooling rate of the cooling calcination treatment is 2 to 15 ℃/min, wherein the cooling rate can be 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min or 15 ℃/min, and the like, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the cut-off temperature of the temperature-reducing calcination treatment is 5 to 35 ℃, wherein the cut-off temperature can be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the atmosphere of the calcination treatment includes an ammonia gas atmosphere.
As a preferred embodiment of the present invention, the pd-containing compound in step (2)2+The ionic solution comprises PdCl2And (3) solution.
Preferably, the PdCl is a metal halide2The concentration of the solution is 0.01-4 mg.mL-1Wherein the concentration may be 0.01mg.mL-1、1mg.mL-1、2mg.mL-1、3mg.mL-1Or 4mg.mL-1And the like, but not limited to the recited values, and other values not recited within the range of values are also applicable.
In a preferred embodiment of the present invention, the nitrogen-doped porous carbon fiber in the step (2) is added in an amount of 50 to 500mg, wherein the amount of the nitrogen-doped porous carbon fiber may be 50mg, 100mg, 150mg, 200mg, 250mg, 300mg, 350mg, 400mg, 450mg, or 500mg, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the drying time in step (2) is 5 to 30 hours, wherein the time can be 5 hours, 10 hours, 15 hours, 20 hours, 25 hours or 30 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the drying treatment is 50 to 90 ℃, wherein the temperature can be 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable embodiment of the present invention, the atmosphere of the reduction treatment in the step (2) is H2and/Ar mixed gas atmosphere.
Preferably, said H2And Ar in a volume ratio of (2-7%): 1, wherein the volume ratio may be 2%: 1. 3%: 1. 4%: 1. 5%: 1. 6%: 1 or 7%: 1, etc., but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
As a preferable technical scheme of the invention, the reduction treatment in the step (2) comprises heating reduction treatment, heat preservation reduction treatment and cooling reduction treatment which are sequentially carried out.
Preferably, the temperature-raising rate of the temperature-raising reduction treatment is 2 to 15 ℃/min, wherein the temperature-raising rate may be 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min or 15 ℃/min, and the like, but is not limited to the recited values, and other values not recited within the range of the values are also applicable.
Preferably, the temperature of the heat-preserving reduction treatment is 200 to 600 ℃, wherein the temperature may be 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time for the heat preservation reduction treatment is 0.5 to 5 hours, wherein the time can be 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the cooling rate of the cooling reduction treatment is 2 to 15 ℃/min, wherein the cooling rate can be 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min or 15 ℃/min, and the like, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) pretreating the imperata cylindrica to obtain a biomass carbon precursor, and sequentially carrying out heating calcination treatment at the heating rate of 2-15 ℃/min, heat preservation calcination treatment at the temperature of 600-1000 ℃ for 0.5-5 h and cooling calcination treatment at the cooling rate of 2-15 ℃/min to obtain nitrogen-doped porous carbon fibers;
(2) placing the nitrogen-doped porous carbon fiber in the step (1) with the addition amount of 50-500 mg in a concentration of 0.01-4 mg/mL-1Pd of2+And sequentially carrying out adsorption, suction filtration and drying treatment for 5-30 h in the ionic solution, heating reduction treatment with the heating rate of 2-15 ℃/min, heat preservation reduction treatment at the temperature of 200-600 ℃ for 0.5-5 h and cooling reduction treatment with the cooling rate of 2-15 ℃/min to obtain the nitrogen-doped porous carbon fiber surface loaded Pd nanoparticles.
The second purpose of the invention is to provide the application of the preparation method of the biomass carbon-based material according to the first purpose, and the preparation method is applied to the field of carbon materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) the biomass cogongrass cone inflorescence resource is rich, cheap and easy to obtain, and the biomass cogongrass cone inflorescence resource is suitable for large-scale production;
(2) the surface of the biomass carbon-based material contains a large number of C-N polar covalent bonds, has a polarization area with rich atomic layers, and has strong adsorption capacity on polar pollutants;
(3) the Pd nano-particles loaded on the surface of the biomass carbon-based material have stronger capability of activating oxygen to generate high-activity oxygen species;
(4) the performance of catalytic oxidation of formaldehyde at room temperature under the synergistic effect of the C-N polar covalent bond on the surface of the biomass carbon-based material and the Pd nanoparticles is excellent;
(5) the biomass carbon-based material prepared by the method has rich porosity and large specific surface area, and provides a larger 'fixing' place for active sites;
(6) the biomass carbon-based material prepared by the method has great application potential in the fields of rare earth industrial wastewater, electrocatalysis, energy storage and the like.
Drawings
Fig. 1 is a scanning electron microscope image of the nitrogen-doped porous carbon fiber of example 1 of the present invention with Pd nanoparticles supported on the surface.
Fig. 2 is a high-resolution transmission electron microscope image of the nitrogen-doped porous carbon fiber of example 1 of the present invention with Pd nanoparticles supported on the surface.
FIG. 3 is an X-ray diffraction spectrum of Pd nanoparticles supported on the surface of nitrogen-doped porous carbon fiber in example 1 of the present invention.
FIG. 4 is an X-ray photoelectron spectrum of Pd nanoparticles supported on the surface of nitrogen-doped porous carbon fiber in example 1 of the present invention.
Fig. 5 is an X-ray photoelectron spectrum of high-resolution N1s of the Pd nanoparticles supported on the surface of the nitrogen-doped porous carbon fiber in example 1 of the present invention.
FIG. 6 shows NH of Pd nanoparticles supported on the surface of nitrogen-doped porous carbon fiber in example 1 of the present invention3Temperature programmed desorption curve diagram.
FIG. 7 shows CO with Pd nanoparticles loaded on the surface of nitrogen-doped porous carbon fiber in example 1 of the present invention2Temperature programmed desorption profile of (a).
Fig. 8 is a nitrogen adsorption-desorption curve of the nitrogen-doped porous carbon fiber in example 1 of the present invention with Pd nanoparticles supported on the surface.
Fig. 9 is a BJH pore size distribution curve of Pd nanoparticles supported on the surface of nitrogen-doped porous carbon fiber in example 1 of the present invention.
Fig. 10 is an in-situ fourier transform infrared spectrum of the Pd nanoparticles supported on the surface of the nitrogen-doped porous carbon fiber in example 1 of the present invention.
FIG. 11 is an X-ray photoelectron spectrum of the nitrogen-doped porous carbon fiber in comparative example 1 of the present invention.
Fig. 12 is an X-ray photoelectron spectrum of high resolution N1s of the nitrogen-doped porous carbon fiber of comparative example 1 of the present invention.
Fig. 13 is a nitrogen adsorption-desorption graph of the nitrogen-doped porous carbon fiber in comparative example 1 of the present invention.
Fig. 14 is a graph showing the BJH pore size distribution of the nitrogen-doped porous carbon fiber in comparative example 1 of the present invention.
Fig. 15 is an X-ray photoelectron spectrum of the nitrogen-doped porous carbon fiber in comparative example 2 of the present invention.
Fig. 16 is an X-ray photoelectron spectrum of high resolution N1s of the nitrogen-doped porous carbon fiber in comparative example 2 of the present invention.
Fig. 17 is a nitrogen adsorption-desorption graph of the nitrogen-doped porous carbon fiber in comparative example 2 of the present invention.
Fig. 18 is a graph showing the BJH pore size distribution of the nitrogen-doped porous carbon fiber in comparative example 2 of the present invention.
Fig. 19 is an X-ray photoelectron spectrum of the nitrogen-doped porous carbon fiber in comparative example 3 of the present invention.
FIG. 20 is an X-ray photoelectron spectrum of high resolution N1s of the nitrogen-doped porous carbon fiber of comparative example 3 of the present invention.
Fig. 21 is a nitrogen adsorption-desorption graph of the nitrogen-doped porous carbon fiber in comparative example 3 of the present invention.
Fig. 22 is a graph showing the BJH pore size distribution of the nitrogen-doped porous carbon fiber in comparative example 3 of the present invention.
FIG. 23 is an X-ray photoelectron spectrum of the porous carbon fiber of comparative example 4 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a biomass carbon-based material, which comprises the following steps:
(1) thoroughly cleaning the collected biomass imperata cone with deionized water, then placing the cleaned imperata cone in a reaction kettle with the volume of 50mL and the lining of polytetrafluoroethylene, carrying out hydrothermal treatment for 16h at 180 ℃, and taking out the primarily carbonized biomass carbon precursor when the temperature of the reaction kettle is reduced to room temperature. The obtained primary product was then dried in the shade for 5 days at room temperature. And (2) placing a proper amount of dried primarily carbonized biomass carbon precursor into a tubular furnace with an ammonia atmosphere, heating to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature at a cooling rate of 10 ℃/min to finally obtain the nitrogen-doped porous carbon fiber.
(2) Weighing 220mg of nitrogen-doped porous carbon fiber, and placing the nitrogen-doped porous carbon fiber in PdCl with the volume of 30mL2In solution (1.33mg mL)-1) After reaching the adsorption equilibrium, the product is filtered, and the collected product is dried for 12 hours in an oven with the temperature of 60 ℃. Finally, the collected precursor is placed in a chamber having H2In a tubular furnace of the/Ar mixed gas, the temperature is raised to 400 ℃ at a temperature rise rate of 5 ℃/min, the temperature is maintained for 1 hour, and then the temperature is lowered to room temperature at a temperature drop rate of 5 ℃/min, so as to obtain the biomass carbon-based material finally, wherein the biomass carbon-based material prepared in this embodiment is the nitrogen-doped porous carbon fiber with Pd nanoparticles loaded on the surface.
In this example, a scanning electron microscope image of the nitrogen-doped porous carbon fiber with Pd nanoparticles supported on the surface is shown in fig. 1, a high-resolution transmission electron microscope image is shown in fig. 2, an X-ray diffraction spectrum is shown in fig. 3, an X-ray photoelectron energy spectrum is shown in fig. 4, an X-ray photoelectron energy spectrum of high-resolution N1s is shown in fig. 5, and an NH energy spectrum of the high-resolution N1s is shown in fig. 53Temperature programmed desorption curve is shown in FIG. 6, CO2The temperature-programmed desorption curve is shown in fig. 7, the nitrogen adsorption-desorption curve is shown in fig. 8, the BJH pore size distribution curve is shown in fig. 9, and the in-situ fourier transform infrared spectrogram is shown in fig. 10.
Example 2
This example excludes PdCl from step (2)2The concentration of the solution was adjusted from 1.33mg mL-1Replacement was 2mg mL-1Otherwise, the conditions were the same as in example 1.
Example 3
This example excludes PdCl from step (2)2The concentration of the solution was adjusted from 1.33mg mL-1Replacement was 0.67mg mL-1Otherwise, the conditions were the same as in example 1.
Example 4
This example excludes PdCl from step (2)2The concentration of the solution was adjusted from 1.33mg mL-1Replacement was 0.33mg mL-1Otherwise, the conditions were the same as in example 1.
Example 5
This example excludes PdCl from step (2)2The concentration of the solution was adjusted from 1.33mg mL-1Replacement was 0.067mg mL-1Otherwise, the conditions were the same as in example 1.
Comparative example 1
The comparative example provides a method for preparing a biomass carbon-based material, comprising:
thoroughly cleaning the collected biomass imperata cone with deionized water, then placing the cleaned imperata cone in a reaction kettle with the volume of 50mL and the lining of polytetrafluoroethylene, carrying out hydrothermal treatment for 16h at 180 ℃, and taking out the primarily carbonized biomass carbon precursor when the temperature of the reaction kettle is reduced to room temperature. The obtained primary product was then dried in the shade for 5 days at room temperature. And (2) placing a proper amount of dried primarily carbonized biomass carbon precursor in a tubular furnace with an ammonia atmosphere, heating to 900 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature at a cooling rate of 10 ℃/min to finally obtain the biomass carbon-based material, wherein the biomass carbon-based material in the comparative example is nitrogen-doped porous carbon fiber. The X-ray photoelectron spectrum of the nitrogen-doped porous carbon fiber in the comparative example is shown in fig. 11, the X-ray photoelectron spectrum of the high-resolution N1s is shown in fig. 12, the nitrogen adsorption-desorption curve is shown in fig. 13, and the BJH pore size distribution curve is shown in fig. 14.
Comparative example 2
The comparative example provides a method for preparing a biomass carbon-based material, comprising:
thoroughly cleaning the collected biomass imperata cone with deionized water, then placing the cleaned imperata cone in a reaction kettle with the volume of 50mL and the lining of polytetrafluoroethylene, carrying out hydrothermal treatment for 16h at 180 ℃, and taking out the primarily carbonized biomass carbon precursor when the temperature of the reaction kettle is reduced to room temperature. The obtained primary product was then dried in the shade for 5 days at room temperature. And (2) placing a proper amount of dried primarily carbonized biomass carbon precursor in a tubular furnace with an ammonia atmosphere, heating to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature at a cooling rate of 10 ℃/min to finally obtain the biomass carbon-based material, wherein the biomass carbon-based material in the comparative example is nitrogen-doped porous carbon fiber. In the comparative example, an X-ray photoelectron spectrum of the nitrogen-doped porous carbon fiber is shown in fig. 15, an X-ray photoelectron spectrum of the high-resolution N1s is shown in fig. 16, a nitrogen adsorption-desorption curve is shown in fig. 17, and a BJH pore size distribution curve is shown in fig. 18.
Comparative example 3
The comparative example provides a method for preparing a biomass carbon-based material, comprising:
thoroughly cleaning the collected biomass imperata cone with deionized water, then placing the cleaned imperata cone in a reaction kettle with the volume of 50mL and the lining of polytetrafluoroethylene, carrying out hydrothermal treatment for 16h at 180 ℃, and taking out the primarily carbonized biomass carbon precursor when the temperature of the reaction kettle is reduced to room temperature. The obtained primary product was then dried in the shade for 5 days at room temperature. And (3) placing a proper amount of dried primarily carbonized biomass carbon precursor in a tubular furnace with an ammonia atmosphere, heating to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature at a cooling rate of 10 ℃/min to finally obtain the biomass carbon-based material, wherein the biomass carbon-based material of the comparative example is nitrogen-doped porous carbon fiber. In the comparative example, an X-ray photoelectron spectrum of the nitrogen-doped porous carbon fiber is shown in fig. 19, an X-ray photoelectron spectrum of the high-resolution N1s is shown in fig. 20, a nitrogen adsorption-desorption curve is shown in fig. 21, and a BJH pore size distribution curve is shown in fig. 22.
Comparative example 4
The comparative example provides a method for preparing a biomass carbon-based material, comprising:
thoroughly cleaning the collected biomass imperata cone with deionized water, then placing the cleaned imperata cone in a reaction kettle with the volume of 50mL and the lining of polytetrafluoroethylene, carrying out hydrothermal treatment for 16h at 180 ℃, and taking out the primarily carbonized biomass carbon precursor when the temperature of the reaction kettle is reduced to room temperature. The obtained primary product was then dried in the shade for 5 days at room temperature. And (2) placing a proper amount of dried primarily carbonized biomass carbon precursor into a tubular furnace with an argon atmosphere, heating to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature at a cooling rate of 10 ℃/min to finally obtain the biomass carbon-based material, wherein the biomass carbon-based material in the comparative example is porous carbon fiber. An X-ray photoelectron spectrum of the porous carbon fiber of the present comparative example is shown in fig. 23.
The figures provided in the examples and comparative examples are analysed: as can be seen from fig. 1, the size of the nitrogen-doped porous carbon fiber of example 1 is on the micrometer scale; as can be seen from fig. 2, the high-resolution transmission electron microscope image of example 1 shows that Pd nanoparticles with uniform size are uniformly distributed on the surface of the nitrogen-doped porous carbon fiber; as can be seen from fig. 3, the nitrogen-doped porous carbon fiber in example 1 has a wider broad peak near 25 °, which indicates that the prepared carbon fiber is mainly amorphous, while three other characteristic peaks are found near 40 °, 47 ° and 68 °, which correspond to the (111), (200) and (220) crystal planes of Pd (PDF #65-2867), respectively, indicating that Pd nanoparticles are successfully supported on the surface of the nitrogen-doped porous carbon fiber; as can be seen from fig. 4, the surface of the sample prepared in example 1 contains signal peaks of four elements, namely carbon, oxygen, nitrogen and palladium; as can be seen from fig. 5, the nitrogen element doped in example 1 mainly exists on the surface of the porous carbon in a pyridine type nitrogen, pyrrole type nitrogen and graphite type nitrogen structure;
as can be seen from FIG. 6, NH3TPD curves showing the presence of the corresponding NH in the range from 100 ℃ to 300 ℃ and from 310 ℃ to 550 ℃3Indicates that the sample surface contains weak acid and medium strong acid sites; as can be seen from FIG. 7, the nitrogen-doped porous carbon fiber CO in example 12TPD curves show stronger CO at 195 ℃ and 435 ℃ as centers2A desorption peak indicates that weak base and medium strong base sites exist on the surface of the prepared sample; as can be seen from FIG. 8, the BET surface area of the nitrogen-doped porous carbon fiber sample in example 1 is as high as 641.7m2g-1Provides an important 'place' for constructing an active site; as can be seen from fig. 9, according to the BJH pore size distribution curve of the sample prepared in example 1, it can be observed that the pore size of the prepared sample is mainly mesoporous, and the pore size range of the prepared sample is mainly concentrated in the range of 3.0nm to 5.0nm, and the abundant mesoporous structure can effectively increase the adsorption rate of formaldehyde on the surface of the sample;
as can be seen from fig. 10, the in-situ fourier transform infrared spectrum of the Pd nanoparticles supported on the surface of the nitrogen-doped porous carbon fiber prepared in example 1 is shown. As shown in fig. 10, at 1359cm-1、1562cm-1、2868cm-1Where a distinct peak appears, which may be attributed to v of the formate speciess(COO),νas(COO) and ν (CH) peak shaking. In addition, 1463cm-1Peak at and delta (CH) in DOM species2) The vibration peaks are related. These results show that the sample prepared in example 1 is effective in catalytically oxidatively decomposing formaldehyde.
As can be seen from fig. 11, the sample prepared in comparative example 1 has signal peaks of three elements of carbon, oxygen and nitrogen on the surface; as can be seen from fig. 12, the nitrogen element doped in the sample prepared in comparative example 1 exists on the surface of the porous carbon mainly in the pyridine type nitrogen, pyrrole type nitrogen and graphite type nitrogen structures; as can be seen from FIG. 13, the BET surface area of the sample prepared in comparative example 1 was as high as 1085.9m2 g-1Provides an important 'place' for constructing an active site; as can be seen from fig. 14, according to the BJH pore size distribution curve of the sample prepared in comparative example 1, it can be observed that the pore size of the prepared sample is mainly mesoporous, and the pore size range of the prepared sample is mainly concentrated in the range of 3.0nm to 5.0nm, and the abundant mesoporous structure can effectively increase the adsorption rate of formaldehyde on the surface of the sample;
as can be seen from fig. 15, the sample prepared in comparative example 2 has signal peaks of three elements of carbon, oxygen and nitrogen on the surface; as can be seen from fig. 16, the nitrogen element doped in the sample prepared in comparative example 2 exists on the surface of the porous carbon mainly in the pyridine type nitrogen, pyrrole type nitrogen and graphite type nitrogen structures; as can be seen from FIG. 17, the BET surface area of the sample prepared in comparative example 2 was as high as 616.3m2 g-1To build activitySites provide important "sites"; as can be seen from fig. 18, according to the BJH pore size distribution curve of the sample prepared in comparative example 2, it can be observed that the pore size of the prepared sample is mainly mesoporous, the pore size range of the prepared sample is mainly concentrated in the range of 3.0nm to 5.0nm, and the adsorption rate of formaldehyde on the surface of the sample can be effectively increased by the abundant mesoporous structure;
as can be seen from fig. 19, the sample prepared in comparative example 3 has signal peaks of three elements of carbon, oxygen and nitrogen on the surface; as can be seen from fig. 20, the nitrogen element doped in the sample prepared in comparative example 3 exists on the surface of the porous carbon mainly in the pyridine type nitrogen, pyrrole type nitrogen and graphite type nitrogen structures; as can be seen from FIG. 21, the BET surface area of the sample prepared in comparative example 3 was as high as 347.8m2 g-1Provides an important 'place' for constructing an active site; as can be seen from fig. 22, according to the BJH pore size distribution curve of the sample prepared in comparative example 3, it can be observed that the pore size of the prepared sample is mainly mesoporous, and the pore size range of the prepared sample is mainly concentrated in the range of 3.0nm to 5.0nm, and the abundant mesoporous structure can effectively increase the adsorption rate of formaldehyde on the surface of the sample;
as can be seen from fig. 23, the sample surface prepared in comparative example 4 contains only signal peaks of two elements, carbon and oxygen.
The materials prepared in examples 1 to 5 and comparative examples 1 to 4 were subjected to a formaldehyde removal performance test, and the test results are shown in table 1.
The test for evaluating the formaldehyde removal rate was a closed static experimental apparatus using a 6L volume organic glass reactor. First, 100mg of a sample to be tested was evenly spread in a glass petri dish, and then a quartz cover was covered and placed in an organic glass reactor. Next, a certain amount of formaldehyde solution was injected into the reactor by a micro-syringe, and when the concentration of formaldehyde in the reactor was about 500ppm, the lid above the petri dish was opened. The concentration of formaldehyde and carbon dioxide in the whole reaction system is monitored in real time by an infrared photoacoustic spectrometry gas monitor (Innova 1412 i).
TABLE 1
Formaldehyde removal rate (%) Amount of carbon dioxide generated (ppm)
Example 1 96.3 736.8
Example 2 96.5 746.5
Example 3 96.7 709.5
Example 4 89.0 519.8
Example 5 61.8 135.6
Comparative example 1 41.9 3.6
Comparative example 2 49.3 11.0
Comparative example 3 29.4 3.3
Comparative example 4 11.2 6.6
The following rules can be seen from the above table: (1) the nitrogen-rich structure on the surface of the nitrogen-doped porous carbon fiber has a good adsorption effect on formaldehyde; (2) the loaded Pd nano-particles play an important role in the process of catalyzing and degrading formaldehyde; (3) as the content of the supported Pd nanoparticles in the sample increases, the corresponding ability to catalyze the oxidation of formaldehyde also increases; (4) when the content of the supported Pd nanoparticles in the sample increases to a certain extent, the corresponding increase rate of the catalytic formaldehyde oxidation performance also becomes slow. Finally, it should be noted that when a sample with excellent catalytic performance is placed in a reactor to catalytically oxidize formaldehyde, the concentration of carbon dioxide generated in the reaction system is higher than the initial concentration of formaldehyde, which may be attributed to the following two reasons: firstly, the inner wall of the reactor can adsorb a part of formaldehyde, and when the formaldehyde in the system is oxidized and decomposed by the catalyst, the formaldehyde adsorbed on the inner wall of the reactor can be released, and further is catalyzed and converted into carbon dioxide and water by the catalyst; secondly, the formaldehyde solution can form solid paraformaldehyde in the volatilization process, the formed paraformaldehyde can slowly release additional gaseous formaldehyde in the process of catalytic oxidation of formaldehyde, so that the formaldehyde is catalytically oxidized by a sample and converted into carbon dioxide and water, and finally the concentration of the generated carbon dioxide in a reaction system is higher than the initial concentration of the formaldehyde.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The preparation method of the biomass carbon-based material is characterized by comprising the following steps of:
(1) pretreating the imperata cylindrica to obtain a biomass carbon precursor, and calcining the obtained biomass carbon precursor to obtain nitrogen-doped porous carbon fibers;
(2) placing the nitrogen-doped porous carbon fiber obtained in the step (1) into a carbon containing pd2+And sequentially performing adsorption, suction filtration, drying and reduction treatment in the ionic solution to obtain the biomass carbon-based material.
2. The method according to claim 1, wherein the pretreatment of the step (1) comprises washing the anthodium cylindricum with deionized water, and subjecting the washed anthodium cylindricum to a hydrothermal reaction;
preferably, the hydrothermal reaction is carried out using a polytetrafluoroethylene-lined reaction vessel;
preferably, the volume of the reaction kettle in the hydrothermal reaction is 20-150 mL;
preferably, the temperature of the hydrothermal reaction is 120-200 ℃;
preferably, the hydrothermal reaction time is 5-20 h.
3. The preparation method according to claim 1 or 2, wherein the drying time of the biomass carbon precursor in the step (1) at room temperature is 2-8 days;
preferably, the room temperature drying temperature is 5-35 ℃.
4. The production method according to any one of claims 1 to 3, wherein the calcination treatment in step (1) includes a temperature-raising calcination treatment, a temperature-maintaining calcination treatment and a temperature-lowering calcination treatment which are sequentially performed;
preferably, the heating rate of the heating calcination treatment is 2-15 ℃/min;
preferably, the temperature of the heat preservation calcining treatment is 600-1000 ℃;
preferably, the time of the heat preservation calcination treatment is 0.5-5 h;
preferably, the cooling rate of the cooling calcination treatment is 2-15 ℃/min;
preferably, the final temperature of the temperature reduction calcination treatment is 5-35 ℃;
preferably, the atmosphere of the calcination treatment includes an ammonia gas atmosphere.
5. The process according to any one of claims 1 to 4, wherein the pd is contained in the step (2)2+The ionic solution comprises PdCl2A solution;
preferably, the PdCl is a metal halide2The concentration of the solution is 0.01-4 mg.mL-1。
6. The production method according to any one of claims 1 to 5, wherein the nitrogen-doped porous carbon fiber in the step (2) is added in an amount of 50 to 500 mg;
preferably, the drying treatment time in the step (2) is 5-30 h;
preferably, the temperature of the drying treatment is 50-90 ℃.
7. The production method according to any one of claims 1 to 6, wherein the atmosphere of the reduction treatment in the step (2) is H2A mixed gas atmosphere of/Ar;
preferably, said H2And Ar in a volume ratio of (2-7%): 1.
8. the production method according to any one of claims 1 to 7, wherein the reduction treatment in the step (2) includes a temperature-raising reduction treatment, a temperature-keeping reduction treatment and a temperature-lowering reduction treatment which are sequentially performed;
preferably, the heating rate of the heating reduction treatment is 2-15 ℃/min;
preferably, the temperature of the heat preservation reduction treatment is 200-600 ℃;
preferably, the time of the heat preservation reduction treatment is 0.5-5 h;
preferably, the cooling rate of the cooling reduction treatment is 2-15 ℃/min.
9. The method for preparing a composite material according to any one of claims 1 to 8, comprising the steps of:
(1) pretreating the imperata cylindrica to obtain a biomass carbon precursor, and sequentially carrying out heating calcination treatment at the heating rate of 2-15 ℃/min, heat preservation calcination treatment at the temperature of 600-1000 ℃ for 0.5-5 h and cooling calcination treatment at the cooling rate of 2-15 ℃/min on the obtained biomass carbon precursor to obtain nitrogen-doped porous carbon fibers;
(2) placing the nitrogen-doped porous carbon fiber obtained in the step (1) with the addition amount of 50-500 mg in a medium with the concentration of 0.01-4 mg-1Pd of2+And sequentially carrying out adsorption, suction filtration and drying treatment for 5-30 h in the ionic solution, heating reduction treatment at the heating rate of 2-15 ℃/min, heat preservation reduction treatment at the temperature of 200-600 ℃ for 0.5-5 h, and cooling reduction treatment at the cooling rate of 2-15 ℃/min to obtain the nitrogen-doped porous carbon fiber surface loaded Pd nanoparticles.
10. Use of the method for preparing biomass carbon-based material according to any one of claims 1 to 9, characterized in that the method is applied in the field of carbon materials for purifying formaldehyde.
CN202210337943.8A 2022-03-31 2022-03-31 Preparation method and application of biomass carbon-based material Pending CN114717690A (en)

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