CN115069283B - Multi-element doped porous carbon nano-sheet composite two-phase TiO 2 Method for preparing hemisphere - Google Patents
Multi-element doped porous carbon nano-sheet composite two-phase TiO 2 Method for preparing hemisphere Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002135 nanosheet Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-hydroxyfuran-2-carbaldehyde Chemical compound OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000630 rising effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 238000004887 air purification Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01J35/39—
-
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B01J35/40—
-
- B01J35/615—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a multi-element doped porous carbon nano-sheet composite two-phase TiO 2 Hemisphere preparation method, the heterojunction is prepared by in-situ compounding N, C and K doped anatase/rutile TiO by N, K doped porous carbon nano-sheet 2 The heterostructure hemisphere consists of the following preparation steps: firstly, mixing D-glucosamine hydrochloride, urea and potassium titanium oxalate, heating and stirring to form uniform liquid, then placing the obtained liquid into a tube furnace, introducing nitrogen, heating to 500-600 ℃ at a heating rate of 1-10 min/DEG C, preserving heat for 1-6h, then preserving heat for 1-6h at a temperature of 750-850 ℃ through temperature programming, and naturally cooling to obtain the porous carbon nano-sheet doped two-phase TiO composite doped with porous carbon nano-sheet 2 Hemispherical photocatalyst. The heterojunction photocatalyst is used for purifying indoor air, degrading organic pollutants in water by photocatalysis and adsorption, preparing hydrogen by water decomposition by visible light photocatalysis, oxidizing 5-hydroxy furfural and preparing a photocatalysis material of a dye sensitized solar cell, and has remarkable photocatalysis activity.
Description
Technical Field
The invention belongs to the field of air purification, and relates to a multi-purpose air purifierMeta-doped porous carbon nano-sheet composite two-phase TiO 2 The preparation method of hemisphere, in particular to an N, C, K doped anatase/rutile TiO in situ composite porous carbon nano-sheet doped with N, O, K 2 A preparation method of heterogeneous porous hemispherical photocatalyst.
Background
With the development of society, the improvement of living standard of people and the acceleration of urban process, the time of people living and working indoors is gradually increased. Thus, indoor air quality has a significant impact on the health of everyone. However, the poor quality decoration material causes the deterioration of indoor air, and the pollutants in the indoor air mainly comprise Volatile Organic Compounds (VOCs) such as formaldehyde, carbon monoxide, nitrogen oxides and the like, so that the long-term contact of the indoor pollutants can seriously harm the health of human beings and induce various diseases. The world health organization reports that air pollution deprives 700 thousands of lives each year, 4.3 thousands of which are closely related to indoor air pollution. Therefore, the method for effectively removing indoor VOCs has important social significance for improving living environment, improving national physique and reducing haze.
The advent of photocatalytic materials clearly provides the most cost-effective solution to the indoor air purification problem. Photocatalytic oxidation is effective in degrading contaminants, and titanium dioxide is (TiO 2 ) The photocatalyst has the advantages of no toxicity, no harm, low price, high catalytic activity and inactive chemical property, and has wide application in the aspects of indoor air purification, organic pollutant degradation, hydrogen production and the like. However, conventional TiO 2 Nanoparticles due to their large band gap (anatase TiO 2 The forbidden bandwidth is about 3.2 eV), the photocatalytic activity can only be realized under the irradiation of ultraviolet light, the visible light is difficult to use, the generated photon-generated carriers are easy to be compounded, and the catalytic efficiency is greatly reduced. Therefore, widening the light response, fully utilizing visible light and reducing the photo-generated carrier recombination is a key problem to be solved by the invention.
The invention comprises the following steps:
the invention aims at preparing TiO in the prior art 2 Only has photocatalytic activity under the irradiation of ultraviolet light, and is difficult to utilize visible light,and easily causes the defects of generated photon-generated carrier recombination and the like, and provides a multi-element doped porous carbon nano-sheet composite two-phase TiO 2 The preparation method of the hemisphere is characterized in that the multielement doped porous carbon nano sheet is compounded with two-phase TiO 2 The hemisphere is in-situ composite N, C and K doped anatase/rutile TiO of N, O and K doped porous carbon nano-sheet 2 The heterogeneous porous hemisphere is used for purifying indoor air, degrading organic pollutants in water by photocatalysis adsorption, and is a photocatalytic material for biomass oxidation such as water hydrogen production by visible light photocatalysis decomposition and 5-hydroxymethylfurfural, and the preparation method comprises the following steps:
(1) Mixing 10-1000mmol of D-glucosamine hydrochloride, 10-1000mmol of urea and 1-100mmol of potassium titanium oxalate, heating and melting in an oil bath at 30-100 ℃, and continuously stirring until uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, heating to 500-600 ℃ at a heating speed of 1-10 min/DEG C in nitrogen atmosphere, preserving heat for 1-6h, then programming to 750-850 ℃ and preserving heat for 1-6h, taking out a sample after naturally cooling to room temperature, and obtaining the multi-element doped porous carbon nano-sheet composite two-phase TiO 2 Hemispherical photocatalyst.
The invention has the advantages that: the method has simple technical process and is completed in one step. The prepared porous carbon nano sheet doped two-phase TiO 2 The hemisphere is in-situ composite N, C and K doped anatase/rutile TiO of N, O and K doped porous carbon nano-sheet 2 Heterostructure hemispheres, the porous composite photocatalyst has high surface area and specific surface up to 297.6m 2 And/g, can provide more active sites, and doping of N, C and K elements is utilized to introduce impurity energy levels. The porous composite photocatalyst can adsorb harmful gas fast, strengthen the absorption of visible light greatly, promote the separation of carrier and raise the photocatalytic efficiency.
The porous carbon nano sheet doped composite two-phase TiO prepared by the method of the invention 2 The hemisphere has high photocatalysis efficiency, and for purifying indoor air, the photocatalysis adsorbs and degrades organic pollutants in water, 5-hydroxymethyl branThe biomass such as aldehyde has good photocatalytic activity for oxidizing and preparing hydrogen by decomposing water through visible light photocatalysis. And can also be used for preparing dye sensitized solar cells.
Drawings
FIG. 1 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 XRD pattern of hemisphere.
FIG. 2 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 SEM photographs of hemispheres at different angles.
FIG. 3 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 TEM photographs and HRTEM photographs of hemispheres at different multiples.
FIG. 4 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 A STEM-HADDF photograph of a hemisphere and a STEM-mapping photograph of each element.
FIG. 5 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 Hemispherical nitrogen adsorption and desorption isotherms and pore size distribution plots.
FIG. 6 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the methods of the first and second embodiments of the present invention 2 Hemispheres and comparative example one of the catalysts prepared as described above was used to photocatalyst the conversion rate profile of air-purifying formaldehyde.
FIG. 7 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the methods described in the first and second embodiments of the present invention 2 Hemispheres and comparative example one catalyst prepared as described in>A graph of the hydrogen production rate of photocatalytic water splitting under the irradiation of 420nm visible light.
FIG. 8 shows a doped porous carbon nanoplate composite doped two-phase TiO prepared by the method of embodiment 2 Hemispherical in>And the photocatalytic water splitting to produce hydrogen under the irradiation of 420nm visible light has the circulation stability.
Detailed Description
The invention is illustrated in further detail by the following examples:
embodiment one:
(1) Mixing 20mmol of D-glucosamine hydrochloride, 80mmol of urea and 1.7mmol of potassium titanium oxalate, heating in an oil bath at 75 ℃, and continuously stirring until a uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 550 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 4 hours, then heating to 850 ℃ by a program, preserving heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase composite TiO doped with the porous carbon nano-sheet 2 Hemispherical photocatalyst.
Embodiment two:
(1) Mixing 20mmol of D-glucosamine hydrochloride, 80mmol of urea and 1.7mmol of potassium titanium oxalate, heating in an oil bath at 75 ℃, and continuously stirring until a uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 500 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 2h, then preserving heat for 4h by programming to 750 ℃, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase composite TiO 2 Hemispherical photocatalyst.
Embodiment III:
(1) Mixing 20mmol of D-glucosamine hydrochloride, 160mmol of urea and 3.4mmol of potassium titanium oxalate, heating in an oil bath at 50 ℃, and continuously stirring until a uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 550 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 4 hours, then heating to 850 ℃ by a program, preserving heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase composite TiO doped with the porous carbon nano-sheet 2 A micro-light catalyst.
Embodiment four:
(1) Mixing 60mmol of D-glucosamine hydrochloride, 800mmol of urea and 20mmol of potassium titanium oxalate, heating in an oil bath at 75 ℃, and continuously stirring until a uniform liquid is formed;
(2) Will step by stepPouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 550 ℃ at a heating speed of 10 min/DEG C, preserving heat for 4 hours, heating to 850 ℃ by a program, preserving heat for 6 hours, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase TiO composite doped with the porous carbon nano-sheet 2 Hemispherical photocatalyst.
Fifth embodiment:
(1) Mixing 100mmol of D-glucosamine hydrochloride, 800mmol of urea and 50mmol of potassium titanium oxalate, heating in an oil bath at 80 ℃, and continuously stirring until a uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 600 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 4 hours, then heating to 900 ℃ by a program, preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase TiO composite doped with the porous carbon nano-sheet 2 Hemispherical photocatalyst.
Example six:
(1) Mixing 20mmol of D-glucosamine hydrochloride, 80mmol of urea and 1.7mmol of potassium titanium oxalate, heating in an oil bath at 75 ℃, and continuously stirring until a uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 550 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 4 hours, then heating to 850 ℃ by a program, preserving heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase composite TiO doped with the porous carbon nano-sheet 2 Hemispherical photocatalyst.
Embodiment seven:
(1) Mixing 20mmol of D-glucosamine hydrochloride, 80mmol of urea and 1.7mmol of potassium titanium oxalate, heating in an oil bath at 75 ℃, and continuously stirring until a uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing Ar gas, heating to 550 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 4 hours, then heating to 850 ℃ by a program, preserving heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the porous carbon nano-sheet doped two-phase composite TiO 2 Hemispherical photocatalyst.
Comparative example one:
(1) 20mmol of D-glucosamine hydrochloride, 80mmol of urea and 1.7mmol of potassium titanium oxalate were uniformly dispersed in 35mL of water, transferred to a 45mL reaction kettle, and reacted in an oven at 180 ℃ for 6 hours. Taking out the reaction kettle, and naturally cooling to room temperature. Then washing with deionized water and absolute ethyl alcohol respectively, and drying;
(2) Placing the sample obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, introducing nitrogen, heating to 550 ℃ at a temperature rising speed of 10 min/DEG C, preserving heat for 4 hours, then heating to 850 ℃ by a program, preserving heat for 4 hours, naturally cooling to room temperature, and taking out to obtain anatase type TiO 2 A photocatalyst.
FIG. 1 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 XRD pattern of hemisphere. As can be seen from the figure, the resulting TiO 2 TiO in C photocatalyst 2 There are two crystalline phases, respectively matching anatase (JCPCDS 71-1166) and rutile (JCPCDS 78-1509) TiO 2 . The strong diffraction peaks at 2 theta 25.3 deg., 37.8 deg., 48.0 deg. correspond to anatase TiO respectively 2 The (101), (004), (200) crystal planes. The strong diffraction peaks at 27.4 ° and 54.3 ° for 2θ correspond to the (110) and (211) crystal planes of the rutile type, respectively. XRD patterns demonstrate rutile and anatase phases of TiO in the sample 2 Is present. Except for TiO 2 Outside the peak of (2), in TiO 2 No other diffraction peaks were observed in/C, indicating that there were no other impurities in the synthesized samples. It is possible that there is no significant carbon peak because the diffraction peak intensity of TiO2 is too strong and the carbon obtained is amorphous carbon.
FIG. 2 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 SEM photographs of hemispheres at different angles. As can be seen from figure a, tiO 2 The nano particles are uniformly dispersed on the carbon nano sheet, and the side photograph of the graph b shows that hemispherical TiO is uniformly anchored on the carbon nano particles 2 And (3) nanoparticles. Hemispheres with outward cross sections can also be seen.
FIG. 3 shows a multi-component blend prepared by the method of embodiment one of the present inventionHybrid porous carbon nano-sheet composite two-phase TiO 2 TEM photographs and HRTEM photographs of hemispheres at different multiples. As can be seen from the figure, tiO 2 The nanometer hemispherical particles are uniformly dispersed on the carbon nanometer sheet, and TiO 2 The diameter of the particles was about 150nm. The enlarged photograph of FIG. b shows TiO 2 The nanoparticles are tightly anchored to the carbon nanoplatelets. FIG. c shows that the samples obtained in example I have lattice spacings of 0.35nm and 0.25nm, corresponding to the (101) and (101) planes of anatase and rutile, respectively, further confirm the formation of the anatase/rutile phase and that from the figure it can be seen that the rutile phase is TiO 2 Anatase phase TiO 2 Is in close contact, which facilitates the migration of photogenerated carriers.
FIG. 4 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 A STEM-HADDF photograph of a hemisphere and a STEM-mapping photograph of each element. From the figure, five elements of Ti, O, C, N and K are uniformly distributed.
FIG. 5 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 Hemispherical N2 adsorption and desorption isotherms and pore size distribution plots. The BET specific surface area obtained was 297.6m 2 /g。
FIG. 6 shows a multi-doped porous carbon nanoplatelets composite two-phase TiO prepared by the method of example one and comparative example one of the present invention 2 Hemispheres and comparative example one catalyst prepared as described in>A graph of the conversion rate of photocatalytic air purification formaldehyde under irradiation of 420nm visible light. As can be seen from the graph, the degradation rate of the sample obtained in the first example, which utilizes visible light to degrade formaldehyde for 30min, is close to 100%, and is far superior to the photocatalytic degradation efficiency of the sample obtained in the first comparative example.
FIG. 7 shows a multi-doped porous carbon nanoplatelets composite two-phase TiO prepared by the method of example one and comparative example one of the present invention 2 Hemispheres and comparative example one catalyst prepared as described in>A graph of the hydrogen production rate of photocatalytic water splitting under the irradiation of 420nm visible light. Hydrogen production rate after six hours under visible light irradiation. As can be seen from the figure, the samples obtained in example one and comparative example one were producedThe hydrogen rates were 28.7 and 0.98mmol/g/h, respectively, and the hydrogen production rate of the sample obtained in example one was far higher than that of the sample obtained in comparative example one.
FIG. 8 shows a multi-component porous carbon nano-sheet composite two-phase TiO prepared by the method of the embodiment 2 Hemispherical in>And the photocatalytic water splitting to produce hydrogen under the irradiation of 420nm visible light has the circulation stability. As can be seen from the graph, after 4 cycles, the hydrogen production was hardly decreased.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above examples, and any other changes, substitutions, simplifications, etc. made without departing from the principles of the present invention and the technical process are all equivalent substitutions and should be included in the protection scope of the present invention.
Claims (1)
1. Multi-element doped porous carbon nano-sheet composite two-phase TiO 2 The preparation method of the hemisphere is characterized in that the multielement doped porous carbon nano sheet is compounded with two-phase TiO 2 The hemisphere is in-situ composite N, C and K doped anatase/rutile TiO of N, O and K doped porous carbon nano-sheet 2 The heterogeneous porous hemisphere is formed, and is used for photocatalytic degradation of formaldehyde in air and photocatalytic material for hydrogen production by photocatalytic decomposition of water by visible light, and the preparation method comprises the following steps:
(1) Mixing 10-100 mmol of D-glucosamine hydrochloride, 10-1000mmol of urea and 1-100mmol of potassium titanium oxalate, heating and melting in an oil bath at 30-100 ℃, and continuously stirring until uniform liquid is formed;
(2) Pouring the liquid obtained in the step (1) into a porcelain boat, then placing the porcelain boat into a tube furnace, heating to 500-600 ℃ at a heating speed of 1-10 min/DEG C in a nitrogen atmosphere, preserving heat for 1-6h, then programming to 750-850 ℃ and preserving heat for 1-6h, taking out the sample after naturally cooling to room temperature, and obtaining the multi-element doped porous carbon nano-sheet composite two-phase TiO 2 Hemispherical photocatalyst.
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