CN115445565B - Copper-doped graphene aerogel for adsorbing VOCs and preparation method thereof - Google Patents
Copper-doped graphene aerogel for adsorbing VOCs and preparation method thereof Download PDFInfo
- Publication number
- CN115445565B CN115445565B CN202210975066.7A CN202210975066A CN115445565B CN 115445565 B CN115445565 B CN 115445565B CN 202210975066 A CN202210975066 A CN 202210975066A CN 115445565 B CN115445565 B CN 115445565B
- Authority
- CN
- China
- Prior art keywords
- copper
- graphene aerogel
- roasting
- doped graphene
- atmosphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 132
- 239000004964 aerogel Substances 0.000 title claims abstract description 70
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 48
- 239000000017 hydrogel Substances 0.000 claims description 40
- 239000010949 copper Substances 0.000 claims description 37
- 239000012298 atmosphere Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000000197 pyrolysis Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 230000004913 activation Effects 0.000 claims description 20
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- SCGJLFGXXZTXSX-UHFFFAOYSA-N copper;ethanol Chemical compound [Cu].CCO SCGJLFGXXZTXSX-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 description 30
- 239000011148 porous material Substances 0.000 description 25
- 238000001994 activation Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000005457 optimization Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 101100109406 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) aga-1 gene Proteins 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- GZTBKEOTCAVWNJ-UHFFFAOYSA-L C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] Chemical compound C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] GZTBKEOTCAVWNJ-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- MWTXLMFPCZIOHL-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Cu+2].C(C)O Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].C(C)O MWTXLMFPCZIOHL-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VGQXTTSVLMQFHM-UHFFFAOYSA-N peroxyacetyl nitrate Chemical compound CC(=O)OO[N+]([O-])=O VGQXTTSVLMQFHM-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01D53/04—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 with stationary adsorbents
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof, and relates to the field of volatile organic compound adsorption materials.
Description
Technical Field
The invention relates to the field of volatile organic compound adsorption materials, in particular to copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) are a generic term for volatile organic compounds having a melting point below room temperature and a boiling point between 50 and 260℃and are commonly known as benzene, toluene, xylene, styrene, trichloroethylene, etc. VOCs are mainly derived from industrial production and social life. The most amount of VOCs produced by industry, such as pharmaceutical industry, petrochemical industry, printing industry, electronic industry, manufacturing industry and the like, is accompanied by a large amount of VOCs. VOCs are toxic, harmful, inflammable and explosive volatile organic matters, are harmful to animals, plants and human beings, and bring certain potential safety hazards to enterprise production due to the inflammable and explosive nature.
Hydrocarbon and nitrogen oxides in VOCs can generate a series of complex photochemical chain reactions under the action of sunlight and ultraviolet rays, and secondary pollution such as ozone, peroxyacetyl nitrate, high-activity free radicals, aldehydes, ketones, organic acids and the like can be generated in the reaction process. In addition, the high-activity free radicals and other intermediate products react with toluene, xylene and the like to generate organic aerosol and haze, so that the ecological environment is further destroyed, and the human health is influenced. Therefore, the efficient treatment of VOCs is particularly important, and among a plurality of VOCs treatment methods, the adsorption method has the advantages of low cost, wide application range, simple and convenient use, no secondary pollution, recycling of the adsorbent and the like, and is widely applied to the field of gas purification. As the core of the adsorption technology, the development of high-performance gas adsorption materials has been a research hotspot in this field.
Although the traditional adsorbents such as activated carbon, silica gel and the like have larger adsorption capacity for VOCs, the adsorption capacity of the materials can be obviously reduced in a humid environment, and the competitive adsorption of water molecules is caused by poor hydrophobicity of the materials. The graphene aerogel has surface functional groups which are easy to adjust, namely, the surface wettability of the graphene aerogel is easy to adjust and control, so that the graphene aerogel can efficiently adsorb VOCs in a humid environment. However, the graphene aerogel has a small specific surface area, a large pore diameter and a small adsorption capacity to VOCs because the graphene aerogel is purely physically adsorbed.
Disclosure of Invention
The invention aims to provide copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof, so as to solve the problem that the graphene aerogel has weaker adsorption force on VOCs.
In order to solve the technical problems, the invention adopts the following specific scheme: a copper doped graphene aerogel for adsorbing VOCs comprises graphene aerogel and nano copper loaded on the graphene aerogel.
The preparation method of the copper-doped graphene aerogel comprises the following steps: and cleaning and impregnating the graphene hydrogel with a copper salt ethanol aqueous solution, freeze-drying after impregnation, performing pyrolysis roasting on the gel subjected to freeze drying in an inert atmosphere, and finally performing activation roasting in an activation atmosphere containing carbon dioxide to obtain the copper-doped graphene aerogel.
As a further optimization of the above technical scheme, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
As a further optimization of the above technical scheme, the activating atmosphere is a pure carbon dioxide atmosphere.
As a further optimization of the technical scheme, the activating atmosphere is a mixed atmosphere of carbon dioxide and inert gas, wherein the volume fraction of the carbon dioxide is more than 20%.
As a further optimization of the above technical scheme, the inert gas is nitrogen or argon.
As the technical proposal is further optimized, the pyrolysis roasting temperature is 150-450 ℃ and the roasting time is 1-10 h; the activating roasting temperature is 600-900 ℃ and the roasting time is 1-5 h.
As a further optimization of the above technical scheme, the copper salt in the copper salt ethanol aqueous solution is one of copper nitrate, copper acetate or copper sulfate.
As a further optimization of the technical scheme, the mass fraction of copper salt in the copper salt ethanol aqueous solution is 0.5% -5%, and the volume fraction of ethanol in the copper salt ethanol aqueous solution is 10% -20%.
As a further optimization of the technical scheme, the graphene hydrogel is washed 5-15 times by copper salt ethanol aqueous solution, is immersed for 12-36 hours, and is subjected to freeze drying for 24-72 hours after the immersion is completed.
As a further optimization of the above technical scheme, the graphene hydrogel is prepared by the following method: and ultrasonically dispersing graphene oxide in an aqueous solution to prepare graphene oxide dispersion liquid, adding a reducing agent, stirring, and performing a heating reaction to obtain the graphene hydrogel.
As a further optimization of the technical scheme, the reducing agent is one of ethylenediamine, ascorbic acid or hydrazine hydrate.
As further optimization of the technical scheme, the mass ratio of the reducing agent to the graphene oxide is 0.5-2:1.
As a further optimization of the technical scheme, the concentration of the graphene oxide dispersion liquid is 0.5-10g/L, and the ultrasonic treatment time is 10-90 min.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a modification method of graphene aerogel, which comprises the steps of impregnating copper salt with the graphene aerogel, preparing copper-doped graphene aerogel through two-stage roasting, and carrying out copper salt pyrolysis and CO 2 The activation process acts together to greatly increase the micropore structure of the graphene aerogel, and copper is introduced as a chemical adsorption active center to greatly increase the saturated adsorption quantity of the graphene aerogel.
The copper-doped graphene aerogel prepared by the method disclosed by the invention has the advantages of small density, large specific surface area, high porosity, multiple micropore structures and the like as a three-dimensional porous aerogel material, and the graphene aerogel has surface functional groups which are easy to adjust, namely, the surface wettability of the graphene aerogel is easy to adjust and control, so that the graphene aerogel can efficiently adsorb VOCs in a humid environment.
Detailed Description
Example 1
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel for 10 times by using a copper acetate ethanol water solution with the mass fraction of copper acetate being 1% and the volume fraction of ethanol being 20%, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 24 hours after washing. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The first stage roasting is pyrolysis roasting, the temperature is 350 ℃, the heating rate is 5 ℃/min, the roasting time is 4 hours, and the pyrolysis roasting atmosphere is nitrogen; the second stage of roasting is activation roasting, the temperature is 800 ℃, the heating rate is 5 ℃/min, the roasting time is 2 hours, the activation roasting atmosphere is a mixed gas of carbon dioxide and nitrogen, and the volume fraction of the carbon dioxide is 30%. And cooling to room temperature after roasting to obtain the copper-doped graphene aerogel (Cu/AGA-1).
The specific surface area and the pore diameter of Cu/AGA-1 are analyzed to obtain the Cu/AGA-1 with the specific surface area of 524.9m 2 And/g, average pore diameter of 2.1nm.
Example 2
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel with a copper nitrate aqueous solution with the mass fraction of copper nitrate being 1% and the volume fraction of ethanol being 20% for 10 times, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and after washing, the solution is used for soaking for 24 hours. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The first stage roasting is pyrolysis roasting, the temperature is 350 ℃, the heating rate is 5 ℃/min, the roasting time is 4 hours, and the pyrolysis roasting atmosphere is nitrogen; the second stage of roasting is activation roasting, the temperature is 800 ℃, the heating rate is 5 ℃/min, the roasting time is 2 hours, the activation roasting atmosphere is a mixed gas of carbon dioxide and nitrogen, and the volume fraction of the carbon dioxide is 30%. And cooling to room temperature after roasting to obtain the copper-doped graphene aerogel (Cu/AGA-2).
The specific surface area and the pore diameter of Cu/AGA-2 are analyzed to obtain the Cu/AGA-2 with the specific surface area of 450.8m 2 And/g, average pore diameter of 3.2nm.
Example 3
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel for 10 times by using a copper sulfate ethanol water solution with the mass fraction of copper sulfate being 1% and the volume fraction of ethanol being 20%, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 24 hours after the washing is finished. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The first stage roasting is pyrolysis roasting, the temperature is 350 ℃, the heating rate is 5 ℃/min, the roasting time is 4 hours, and the pyrolysis roasting atmosphere is nitrogen; the second stage of roasting is activation roasting, the temperature is 800 ℃, the heating rate is 5 ℃/min, the roasting time is 2 hours, the activation roasting atmosphere is a mixed gas of carbon dioxide and nitrogen, and the volume fraction of the carbon dioxide is 30%. And cooling to room temperature after roasting to obtain the copper-doped graphene aerogel (Cu/AGA-3).
The specific surface area and the pore diameter of Cu/AGA-3 are analyzed to obtain the specific surface area of 413.2m 2 And/g, average pore diameter of 3.4nm.
Example 4
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel for 10 times by using a copper acetate ethanol water solution with the mass fraction of copper acetate being 1% and the volume fraction of ethanol being 20%, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 24 hours after washing. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The first stage roasting is pyrolysis roasting, the temperature is 350 ℃, the heating rate is 5 ℃/min, the roasting time is 4 hours, and the pyrolysis roasting atmosphere is nitrogen; the second stage of roasting is activation roasting, the temperature is 800 ℃, the heating rate is 5 ℃/min, the roasting time is 2h, and the activation roasting atmosphere is carbon dioxide atmosphere. And cooling to room temperature after roasting to obtain the copper-doped graphene aerogel (Cu/AGA-4).
The specific surface area and the pore diameter of Cu/AGA-4 are analyzed to obtain the Cu/AGA-4 with the specific surface area of 518.9m 2 And/g, average pore diameter of 2.5nm.
Example 5
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.02g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 10min to obtain 0.5g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ethylenediamine into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel with a copper acetate aqueous solution with the mass fraction of copper acetate being 0.5% and the volume fraction of ethanol being 10% for 15 times, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and after washing, the solution is used for soaking for 12 hours. The impregnated hydrogel was freeze-dried for 36h and placed in a tube furnace for calcination. The first stage roasting is pyrolysis roasting, the temperature is 350 ℃, the heating rate is 5 ℃/min, the roasting time is 4 hours, and the pyrolysis roasting atmosphere is nitrogen; the second stage of roasting is activation roasting, the temperature is 800 ℃, the heating rate is 5 ℃/min, the roasting time is 2 hours, the activation roasting atmosphere is a mixed gas of carbon dioxide and nitrogen, and the volume fraction of the carbon dioxide is 30%. And cooling to room temperature after roasting is finished to obtain the Cu/AGA of the copper-doped graphene aerogel.
Example 6
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.4g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 90min to obtain 10g/L graphene oxide dispersion liquid.
(2) Adding 0.2g of hydrazine hydrate into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL of the mixture, placing the 10mL of the mixture into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel with a copper acetate ethanol water solution with the mass fraction of copper acetate being 5% and the volume fraction of ethanol being 15% for 5 times, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 36 hours after washing. Freeze-drying the impregnated hydrogel for 24 hours, and placing the hydrogel into a tube furnace for roasting. The first stage roasting is pyrolysis roasting, the temperature is 450 ℃, the heating rate is 10 ℃/min, the roasting time is 1h, and the pyrolysis roasting atmosphere is nitrogen; the second stage of roasting is activation roasting, the temperature is 900 ℃, the heating rate is 10 ℃/min, the roasting time is 1h, the activation roasting atmosphere is a mixed gas of carbon dioxide and nitrogen, and the volume fraction of the carbon dioxide is 20%. And cooling to room temperature after roasting is finished to obtain the Cu/AGA of the copper-doped graphene aerogel.
Example 7
A copper-doped graphene aerogel for adsorbing VOCs and a preparation method thereof specifically comprise the following steps:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel for 10 times by using a copper acetate ethanol water solution with the mass fraction of copper acetate being 1% and the volume fraction of ethanol being 20%, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 24 hours after washing. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The first stage roasting is pyrolysis roasting, the temperature is 150 ℃, the heating rate is 5 ℃/min, the roasting time is 10h, and the pyrolysis roasting atmosphere is argon; the second stage of roasting is activation roasting, the temperature is 600 ℃, the heating rate is 5 ℃/min, the roasting time is 5h, the activation roasting atmosphere is a mixed gas of carbon dioxide and argon, and the volume fraction of the carbon dioxide is 20%. And cooling to room temperature after roasting is finished to obtain the Cu/AGA of the copper-doped graphene aerogel.
Comparative example 1
The copper-doped graphene aerogel (Cu/GA-1) without second stage firing was taken as comparative example 1, and the specific steps were as follows:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel for 10 times by using a copper acetate ethanol water solution with the mass fraction of copper acetate being 1% and the volume fraction of ethanol being 20%, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 24 hours after washing. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The roasting temperature is 350 ℃, the heating rate is 5 ℃/min, the roasting time is 4 hours, and the roasting atmosphere is nitrogen. And cooling to room temperature after roasting to obtain the Cu/GA of the copper-doped graphene aerogel.
The specific surface area and pore size of Cu/GA-1 were analyzed to obtain 362.1m2/g of specific surface area and 3.6nm of average pore size.
Comparative example 2
Copper-doped graphene aerogel (Cu/GA-2) without first stage firing was taken as comparative example 2, and the specific steps were as follows:
(1) 0.4g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.4g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And (3) washing the graphene hydrogel for 10 times by using a copper acetate ethanol water solution with the mass fraction of copper acetate being 1% and the volume fraction of ethanol being 20%, wherein each washing step is carried out for 10 minutes, then a new solution is replaced, and the solution is used for soaking for 24 hours after washing. The impregnated hydrogel was freeze-dried for 72 hours and placed in a tube furnace for calcination. The roasting temperature is 800 ℃, the heating rate is 5 ℃/min, the roasting time is 2h, the roasting atmosphere is a mixed gas of carbon dioxide and nitrogen, and the volume fraction of the carbon dioxide is 30%. And cooling to room temperature after roasting to obtain the copper-doped graphene aerogel Cu/GA-2'.
The Cu/GA-2 weight loss is serious compared with Cu/AGA-1, namely the process has high burning loss rate.
The specific surface area and pore size of Cu/GA-2 were analyzed to obtain a specific surface area of 389.1m2/g and an average pore size of 6.5nm.
Comparative example 3
Graphene Aerogel (GA) was used as comparative example 3, and the specific steps were as follows:
(1) 0.04g of graphene oxide is dispersed in 40mL of aqueous solution, and ultrasonic treatment is carried out for 30min to obtain 1g/L graphene oxide dispersion liquid.
(2) Adding 0.04g of ascorbic acid into the graphene oxide dispersion liquid, stirring for 20min, taking 10mL, placing into a sample bottle, and placing the sample bottle into a 70 ℃ oven for heating reaction for 5h to obtain the graphene hydrogel.
(3) And washing the graphene hydrogel with an ethanol aqueous solution with the volume fraction of 20% for 10 times, wherein the graphene hydrogel is soaked for 10 minutes in each washing, then is replaced with a new solution, and is dialyzed for 24 hours after washing. And freeze-drying the dialyzed hydrogel for 72 hours to obtain Graphene Aerogel (GA).
The GA was analyzed for specific surface area and pore size to give a specific surface area of 233.1m 2 And/g, average pore diameter of 4.4nm.
< evaluation of adsorption Performance of VOCs >
The test was performed using an adsorption evaluation device. By N 2 As carrier gas, N 2 Introducing into VOCs generator, adding toluene into gasification chamber of VOCs generator by injection pump for rapid gasification, and introducing into gasification chamber by N 2 The generator is carried out into the adsorber. The constant temperature adsorber is a glass tube with a jacket, and the adsorption temperature is controlled by adopting a super constant temperature tank. The inside diameter of the adsorber was 10mm, the length was 10cm, and the adsorbent loading was 0.1g. The toluene concentration before and after adsorption was measured by gas chromatography.
Test conditions:
the original concentration of toluene was 500ppm, the total gas flow rate was 100mL/min, and the adsorption temperature was 30 ℃.
Test results:
| sample of | Saturated adsorption quantity (mg/g) |
| Example 1 | 33.5 |
| Example 2 | 22.4 |
| Example 3 | 20.8 |
| Comparative example 1 | 18.6 |
| Comparative example 2 | 13.9 |
| Comparative example 3 | 6.8 |
Studies have shown that the adsorption of VOCs on the aerogel is largely dependent on the micropores of the adsorbent, since the kinetic diameters of VOCs are within the micropore size range.
< analysis of specific surface area and pore Structure >
Comparing the data of example 1, comparative example 1 and comparative example 2, it can be obtained that the specific surface area of Cu/AGA-1 in example 1 is the largest and the average pore diameter is the smallest. The specific mechanism is as follows: the first stage roasting is a copper acetate pyrolysis process, and the GA impregnated copper acetate is decomposed by impurities on the surface and in larger pores of the copper acetate during the pyrolysis process to open a part of closed pores, and in addition, the GA skeleton is contracted to reduce the original pore size, so that the pyrolysis process increases the microporous structure of the graphene aerogel. The second stage roasting is CO 2 Activation process, CO in high temperature environment 2 Has certain oxidability of CO 2 As a gas, compared with Cu, it can enter into the graphene aerogel microporous structure to react more deeply with disordered carbon atoms and heteroatoms therein, further opening the closed pore structure, forming a new microporous pore structure. Copper acetate pyrolysis and CO 2 The activation process works together so that the microporous structure of the aerogel is greatly increased. Comparative example 1 is copper-doped graphene aerogel (Cu/GA-1) without second stage firing, without CO 2 The specific surface area of the activation process is far smaller than that of Cu/AGA-1, and the average pore diameter is also larger. Comparative example 2 is a copper-doped graphene aerogel (Cu/GA-2) without first stage firing, which can be found in CO 2 /N 2 Under a mixed atmosphere (high temperature)The copper acetate has certain oxidizing property), the copper acetate decomposition process is more severe, and the CO is added 2 In the activation process, excessive carbon burning in the aerogel is caused, so that the original pores of the aerogel are increased, and part of micropore structures are converted into mesoporous structures, so that the average pore diameter is larger than that of Cu/AGA-1, and the specific surface area is small.
The atmosphere of pyrolysis roasting is nitrogen atmosphere, the atmosphere of activation roasting is a mixed atmosphere of carbon dioxide and nitrogen, and CO 2 The activation needs to be carried out at very high temperatures (generally greater than 600 ℃), and therefore CO cannot be carried out in this temperature range from 150 to 450 ℃ 2 Activating.
< analysis of copper as principle of chemisorption Activity center >
The product generated by the pyrolysis of copper acetate at 150-300 ℃ is Cu 2 O, then Cu in the process of heating to 400 DEG C 2 O is continuously decomposed into Cu, and the product generated at the temperature of 400-450 ℃ is nano Cu. Toluene has pi bond, cu can absorb pi electron in toluene to form sigma bond, and pi complexing adsorption is formed, wherein pi complexing belongs to weak chemical bond category.
Claims (12)
1. The preparation method of the copper-doped graphene aerogel for adsorbing VOCs is characterized by comprising the steps of cleaning and impregnating graphene hydrogel with copper salt ethanol aqueous solution, freeze-drying after impregnation, performing pyrolysis roasting on the gel after freeze-drying in inert atmosphere, and finally performing activation roasting in activating atmosphere containing carbon dioxide to obtain the copper-doped graphene aerogel;
the activating atmosphere is a mixed atmosphere of carbon dioxide and inert gas, wherein the volume fraction of the carbon dioxide is more than 20%;
the pyrolysis roasting temperature is 150-450 ℃, and the roasting time is 1-10 h; the activation roasting temperature is 600-900 ℃ and the roasting time is 1-5 h;
the mass fraction of copper salt in the copper salt ethanol water solution is 0.5% -5%.
2. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
3. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the activating atmosphere is a pure carbon dioxide atmosphere.
4. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the inert gas is nitrogen or argon.
5. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the copper salt in the copper salt ethanol aqueous solution is one of copper nitrate, copper acetate or copper sulfate.
6. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the volume fraction of ethanol in the copper salt ethanol aqueous solution is 10% -20%.
7. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the graphene hydrogel is washed with copper salt ethanol aqueous solution for 5-15 times, impregnated for 12-36 hours, and freeze-dried for 24-72 hours after the impregnation is completed.
8. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 1, wherein the graphene hydrogel is prepared by the following method: and ultrasonically dispersing graphene oxide in an aqueous solution to prepare graphene oxide dispersion liquid, adding a reducing agent, stirring, and performing a heating reaction to obtain the graphene hydrogel.
9. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 8, wherein the reducing agent is one of ethylenediamine, ascorbic acid or hydrazine hydrate.
10. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 8, wherein the mass ratio of the reducing agent to graphene oxide is 0.5-2:1.
11. The method for preparing copper-doped graphene aerogel for adsorbing VOCs according to claim 8, wherein the concentration of the graphene oxide dispersion liquid is 0.5-10g/L, and the ultrasonic treatment time is 10-90 min.
12. A copper-doped graphene aerogel for adsorbing VOCs, prepared by the method of any one of claims 1 to 11, characterized in that the copper-doped graphene aerogel comprises graphene aerogel and nano-copper supported on the graphene aerogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210975066.7A CN115445565B (en) | 2022-08-15 | 2022-08-15 | Copper-doped graphene aerogel for adsorbing VOCs and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210975066.7A CN115445565B (en) | 2022-08-15 | 2022-08-15 | Copper-doped graphene aerogel for adsorbing VOCs and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115445565A CN115445565A (en) | 2022-12-09 |
| CN115445565B true CN115445565B (en) | 2023-12-01 |
Family
ID=84299309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210975066.7A Active CN115445565B (en) | 2022-08-15 | 2022-08-15 | Copper-doped graphene aerogel for adsorbing VOCs and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115445565B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105253879A (en) * | 2015-11-23 | 2016-01-20 | 国家纳米科学中心 | High-porosity functional graphene material as well as preparation method and applications thereof |
| CN107324454A (en) * | 2017-07-07 | 2017-11-07 | 重庆三峡学院 | A kind of graphene aerogel electrode material for loading copper ion and preparation method thereof |
| CN110327851A (en) * | 2019-06-27 | 2019-10-15 | 中素新科技有限公司 | Elastic graphite alkene aeroge and its preparation method and application |
| CN111003757A (en) * | 2019-11-14 | 2020-04-14 | 中海油天津化工研究设计院有限公司 | Magnetic graphene aerogel particle electrode and preparation method thereof |
| CN113737218A (en) * | 2021-09-29 | 2021-12-03 | 中国石油化工股份有限公司 | Copper-based graphene aerogel composite catalyst, gas diffusion electrode and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8993113B2 (en) * | 2010-08-06 | 2015-03-31 | Lawrence Livermore National Security, Llc | Graphene aerogels |
| CN107913674B (en) * | 2017-10-27 | 2020-08-04 | 苏州大学 | MOF-loaded 3D ruthenium/graphene aerogel composite material, preparation method thereof and application thereof in continuous CO treatment |
-
2022
- 2022-08-15 CN CN202210975066.7A patent/CN115445565B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105253879A (en) * | 2015-11-23 | 2016-01-20 | 国家纳米科学中心 | High-porosity functional graphene material as well as preparation method and applications thereof |
| CN107324454A (en) * | 2017-07-07 | 2017-11-07 | 重庆三峡学院 | A kind of graphene aerogel electrode material for loading copper ion and preparation method thereof |
| CN110327851A (en) * | 2019-06-27 | 2019-10-15 | 中素新科技有限公司 | Elastic graphite alkene aeroge and its preparation method and application |
| CN111003757A (en) * | 2019-11-14 | 2020-04-14 | 中海油天津化工研究设计院有限公司 | Magnetic graphene aerogel particle electrode and preparation method thereof |
| CN113737218A (en) * | 2021-09-29 | 2021-12-03 | 中国石油化工股份有限公司 | Copper-based graphene aerogel composite catalyst, gas diffusion electrode and application |
Non-Patent Citations (4)
| Title |
|---|
| 孟泓杉 ; 王宇晶 ; 张治宏 ; 严乐 ; 杨诗卡 ; .铜掺杂石墨烯气凝胶的制备、表征及在电-芬顿体系中的应用.西安工业大学学报.2018,(03),84-89. * |
| 石墨烯气凝胶复合材料制备及吸附性能的研究进展;钟铠;张弛;仲亚;崔升;沈晓冬;;工业水处理(06);9-14 * |
| 钟铠 ; 张弛 ; 仲亚 ; 崔升 ; 沈晓冬 ; .石墨烯气凝胶复合材料制备及吸附性能的研究进展.工业水处理.2019,(06),9-14. * |
| 铜掺杂石墨烯气凝胶的制备、表征及在电-芬顿体系中的应用;孟泓杉;王宇晶;张治宏;严乐;杨诗卡;;西安工业大学学报(03);84-89 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115445565A (en) | 2022-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jeguirim et al. | Adsorption/reduction of nitrogen dioxide on activated carbons: textural properties versus surface chemistry–a review | |
| Na et al. | High-performance materials for effective sorptive removal of formaldehyde in air | |
| Silvestre-Albero et al. | Ethanol removal using activated carbon: Effect of porous structure and surface chemistry | |
| Liu et al. | Chitosan crosslinked composite based on corncob lignin biochar to adsorb methylene blue: Kinetics, isotherm, and thermodynamics | |
| Mohammed et al. | Adsorption of benzene and toluene onto KOH activated coconut shell based carbon treated with NH3 | |
| Bashkova et al. | The effects of urea modification and heat treatment on the process of NO2 removal by wood-based activated carbon | |
| Belhachemi et al. | Comparison of NO2 removal using date pits activated carbon and modified commercialized activated carbon via different preparation methods: Effect of porosity and surface chemistry | |
| CN102580675B (en) | Modified activated carbon, preparation method thereof and method for adsorbing hydrogen sulfide using modified activated carbon | |
| CN101690888B (en) | A kind of method that utilizes porous mineral to prepare chemical adsorbent | |
| CN110652965B (en) | Semicoke-based activated carbon adsorption material and preparation method and application thereof | |
| CN102627277B (en) | Modified active carbon and method for removing ammonia gas in intensive livestock farm | |
| CA2301697C (en) | Activated carbon filter and process for the separation of noxious gases | |
| Takeuchi et al. | Removal of ozone from air by activated carbon treatment | |
| Lan et al. | Conjugated porous polymers for gaseous toluene adsorption in humid atmosphere | |
| CN111330538A (en) | Activated carbon and preparation method and application thereof | |
| Wang et al. | Preparation of high-performance toluene adsorbents by sugarcane bagasse carbonization combined with surface modification | |
| CN105327699A (en) | Air cleaning material | |
| US20100122515A1 (en) | Poison-filter material and production method thereof | |
| Li et al. | Toluene and water vapor adsorption characteristics and selectivity on hydrophobic resin-based activated carbon | |
| CN115445565B (en) | Copper-doped graphene aerogel for adsorbing VOCs and preparation method thereof | |
| JP2016043296A (en) | catalyst | |
| Yusop et al. | Amoxicillin adsorption onto oil palm trunk‐derived activated carbon: synthesis optimization, modelling of mass transfer and ultrasonic regeneration | |
| KR101369021B1 (en) | Low temperature oxidation catalyst improved water-stability for removal of toxic gases | |
| CN1768924A (en) | An adsorbent for purifying sulfur-containing malodorous waste gas and its preparation method | |
| CN101185876A (en) | Recycled metal/diatomite wastewater treatment agent and its processing technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |