CN105617991A - H-TiO2@N-G/C dual-functional catalytic adsorption material and preparation method and application thereof - Google Patents
H-TiO2@N-G/C dual-functional catalytic adsorption material and preparation method and application thereof Download PDFInfo
- Publication number
- CN105617991A CN105617991A CN201610118641.6A CN201610118641A CN105617991A CN 105617991 A CN105617991 A CN 105617991A CN 201610118641 A CN201610118641 A CN 201610118641A CN 105617991 A CN105617991 A CN 105617991A
- Authority
- CN
- China
- Prior art keywords
- tio
- double
- sorbing material
- function catalyzing
- tio2
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 title abstract description 43
- 230000003197 catalytic effect Effects 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 18
- 238000004513 sizing Methods 0.000 claims description 18
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 17
- 239000005416 organic matter Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003610 charcoal Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 20
- 150000001555 benzenes Chemical class 0.000 abstract description 6
- 150000001299 aldehydes Chemical class 0.000 abstract description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract 2
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 238000010000 carbonizing Methods 0.000 abstract 1
- 229960003638 dopamine Drugs 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003763 carbonization Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930040373 Paraformaldehyde Natural products 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 229920002866 paraformaldehyde Polymers 0.000 description 8
- 229920001690 polydopamine Polymers 0.000 description 7
- 239000002594 sorbent Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000000274 adsorptive effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- -1 halogen hydrocarbon Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229940034040 ethanol / isopropyl alcohol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/633—
-
- 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
Abstract
The invention discloses an H-TiO2@N-G/C dual-functional catalytic adsorption material and a preparation method and application thereof. The method includes the following steps of firstly, adding butyl titanate to selective solvent, dropwise adding the mixture to an ethyl alcohol and water suspension with graphene oxide, and conducting hydrolysis on butyl titanate to generate amorphous form TiO2 to obtain a TiO2@GO material; secondly, dissolving melamine and dopamine in a solution with TiO2@GO according to a certain proportion to prepare a TiO2@GO compound polymer; thirdly, conducting carbonizing and chambering on the TiO2@GO compound polymer to prepare TiO2@N-G/C compound porous carbon with high specific surface; fourthly, putting TiO2@N-G/C in an H2/N2 atmosphere to conduct reduction reaction to finally obtain the H-TiO2@N-G/C dual-functional catalytic adsorption material. The dual-functional catalytic adsorption material is applied for catalysis and adsorption of aldehydes and benzene series volatile organic compounds (VOCs).
Description
Technical field
The invention belongs to porous carbon material field, particularly relate to a kind of H-TiO2N-G/C double-function catalyzing sorbing material and its preparation method and application, volatile organic matter VOCs is had high-selectivity adsorption function by this sorbing material.
Background technology
Porous carbon material is a high efficiency conventional sorbent material of class, and their loading capacity is higher, with low cost but this kind of carbon material surface often has abundant hydrophilic radical (oxy radical), shows stronger wetting ability. Therefore, usually causing its loading capacity significantly to reduce due to the competitive adsorption of vapour molecule in wet environment, especially to volatile organic matter VOCs (such as formaldehyde, acetaldehyde etc.), this problem just becomes particularly to give prominence to. Now there are some researches show: the loading capacity of toluene is reduced by 17% when relative humidity 3.0RH% by gac, when 40.0RH%, the loading capacity of butane is reduced by 30%; Be increased to 60 and 80% when humidity, the adsorptive capacity of VOCs then can be lost 70 and 85% by gac. The major cause causing loading capacity sharply to decline is: hydrophilic radical/element (such as carboxyl or hydroxyl etc.) can be combined with hydrogen bond action with the H atom of water molecules, greatly weaken nonpolar VOCs competitive adsorption power on the sorbent, cause water molecules preferentially to seize activated adsorption position and reduce sorbent material to the loading capacity of volatile organic matter VOCs.
Meanwhile, especially volatile organic matter VOCs is presented with aqueous phase like strong polarity physico-chemical property, greatly reduce sorbent material to the selectivity of volatile organic matter VOCs. Because, if we think that material improves the adsorption to volatile organic matter VOCs, its result must cause material also corresponding to be improved by the adsorption of water molecules, it is very difficult to realize simultaneously material hydrophobic nature and to high-selectivity adsorption volatile organic matter VOCs.
Summary of the invention
The present invention is directed to the situation of above prior art, it is provided that a kind of H-TiO2N-G/C double-function catalyzing sorbing material and its preparation method and application, this H-TiO2N-G/C double-function catalyzing sorbing material, first by volatile organic matter VOCs molecular oxidation under room temperature and no light conditions, and can utilize the weakly alkaline specific surface strengthening of low-pole to the absorption of VOCs oxidation products. Graphitized carbon surface also has hydrophobic nature simultaneously, can improve the anti humility performance of material, and under can solving actual condition, high humidity VOCs gas mixture causes material to the significantly reduction problem of VOCs molecular adsorption capacity due to water molecules competitive adsorption. Current document has no this kind of material report and the report in volatile organic matter VOCs catalytic adsorption content thereof.
The technical scheme of the present invention is achieved in that
A kind of H-TiO2N-G/C double-function catalyzing sorbing material, described H-TiO2N-G/C double-function catalyzing sorbing material has microvoid structure, and described microvoid structure is primarily of content > the greying C of 45wt%, the N of content 6-15wt%, content > TiO of 25wt%2With the 3 D pore canal skeleton of a small amount of O and H element composition; Described H-TiO2The BET specific surface area of N-G/C double-function catalyzing sorbing material is 890-1250m2/ g, described H-TiO2N-G/C double-function catalyzing sorbing material mesoporous < 1.7Micropore volume account for total hole hold volume ratio 60%.
BET:BET Theoretical Calculation be based upon Brunauer, Emmett and Teller tri-people from the multilayer adsorption formula basis that classical statistics theory deduction goes out, namely famous BET equation. This equation is as follows:
P described in formula is adsorbate dividing potential drop; PoFor sorbent material saturated vapor pressure; V is the actual adsorptive capacity of sample; Vm is individual layer saturated extent of adsorption; C is the constant relevant to sample adsorption ability.
A kind of H-TiO as above2The preparation method of N-G/C double-function catalyzing sorbing material, comprises the steps:
(1) butyl (tetra) titanate is dissolved in selective solvent, it is added drop-wise in the aqueous solution containing graphene oxide sheet, butyl (tetra) titanate hydrolysis is generated without sizing TiO2Colloidal sol, described nothing sizing TiO2Colloidal sol can adsorb by oxidized graphene film, obtains TiO2GO material; Described TiO2The structural unit of GO is:
I described in formula is graphene oxide sheet, and II is without sizing TiO2Colloidal sol;
(2) trimeric cyanamide and Dopamine HCL are dissolved into containing TiO2In the aqueous solution of GO material, the oxy radical on graphene oxide sheet surface is polymerized with the amino reaction on trimeric cyanamide TPA and Dopamine HCL PDA, preparation TiO2GO-TPA/PDA; TiO2The skeleton symbol of GO-TPA/PDA is:
The structural unit of the PDA described in formula is:
The structural unit of the TPA described in formula is:
(3) by TiO2GO-TPA/PDA puts into N2The tubular react furnace of atmosphere carries out high-temperature calcination, obtained TiO2N-G/C composite porous charcoal; TiO simultaneously2Make the transition from without sizing to anatase octahedrite. Described TiO2The skeleton symbol of N-G/C composite porous charcoal is:
In formula, III is Detitanium-ore-type TiO2, IV is the compound porous carbon of N-G/C;
(4) by TiO2N-G/C is placed in, at H2/N2Atmosphere carries out reduction reaction, the TiO on composite porous charcoal2It is reduced and generates H-TiO2, finally obtain H-TiO2N-G/C double-function catalyzing sorbing material.
The chemical reaction of step (4) is as follows:
The ultimate principle of the present invention and being contemplated that: in the above-mentioned steps of preparation method of the present invention, step (1) will containing TiO by butyl (tetra) titanate hydrolysis2Load to the catalytic site forming high dispersive on graphene oxide sheet; Step (2) will be by having built H-TiO containing N compound and graphene oxide sheet compound2The basic framework of N-G/C double-function catalyzing sorbing material; Step (3) passes through high-temperature calcination so that TiO2The oxy radical of GO-TPA/PDA material reduces, and greying C/N content increases, simultaneously TiO2Make the transition from without sizing to anatase octahedrite, it is to increase the catalytic activity of catalytic site and the hydrophobic nature of material; TiO in step (4)2Calcining can produce defect and the highly reactive form of oxygen hole of H doping in a hydrogen atmosphere, and this contributes to catalyzer to the transmission of the absorption of chemical oxygen and active oxygen.
Above-described H-TiO2The preparation method of N-G/C double-function catalyzing sorbing material, the mass ratio of the trimeric cyanamide described in described step (2) and Dopamine HCL is 1:(0.5��6); Described trimeric cyanamide and TiO2The mass ratio of GO is 1:(0.1��0.3);
Above-described H-TiO2The preparation method of N-G/C double-function catalyzing sorbing material, calcining temperature described in described step (3) is 400��700 DEG C.
Arbitrary described H-TiO above2The preparation method of N-G/C double-function catalyzing sorbing material, the described butyl (tetra) titanate described in step (1) and the mass ratio of graphene oxide are 1:(0.05��1), the mixed volume of selective solvent and water is than being 1:(0.2��6); The mixing of the one or more than one that described selective solvent is selected from ethanol, ethylene glycol, Virahol. For the present invention, described selective solvent is not restricted to aforesaid cited solvent, from experimental result and binding isotherm, as long as can by amount of carbon atom that butyl (tetra) titanate dissolves lower than 10 lower alcohol can realize the object of the present invention, the aforementioned selection of the present invention is the optimized choice taken into account based on cost and efficiency; The mixed volume of the mass ratio of another butyl (tetra) titanate and graphene oxide, selective solvent and water is the optimized choice taken into account based on cost and efficiency than also, also can realize the object of the present invention outside this scope.
Above-described H-TiO2The preparation method of N-G/C double-function catalyzing sorbing material, it is characterised in that: the reducing atmosphere component H described in step (4)2/N2Volume is 1:(3��9), temperature of reaction is at 200��400 DEG C, and the reaction times is at 0.5��4h. For the present invention, described reducing atmosphere is not restricted to aforesaid cited H2/N2Gas mixture, from experimental result and binding isotherm, as long as the object of the present invention can be able to be realized in the gas mixture of the reducing gas containing H element and rare gas element, the aforementioned selection of the present invention is the optimized choice taken into account based on cost and efficiency; Another H2With N2Mixed volume ratio, calcining temperature are also the optimized choice taken into account based on cost and efficiency, also can realize the object of the present invention outside this scope.
A kind of foregoing H-TiO2The application of N-G/C double-function catalyzing sorbing material, described H-TiO2N-G/C double-function catalyzing sorbing material is applied to the catalysis to volatile organic matter VOCs and absorption.
Foregoing H-TiO2The application of N-G/C double-function catalyzing sorbing material, described H-TiO2N-G/C double-function catalyzing sorbing material is applied in wet environment to the catalysis of volatile organic matter VOCs and absorption.
Described volatile organic matter VOCs, according to the definition boiling point of the World Health Organization at the compound of 50 DEG C-250 DEG C, under room temperature, saturated vapor pressure is more than 133.32Pa, the type organic being present in air at normal temperatures in vapour form. By the difference of its chemical structure, it is possible to be further divided into eight classes: alkane class, aromatic hydrocarbons, alkene class, halogen hydrocarbon class, ester class, aldehyde class, ketone class and other. The main component of general volatile organic matter VOCs has: hydrocarbon class, halohydrocarbon, oxygen hydrocarbon and nitrogen hydrocarbon, and it comprises: benzene series thing, organic chloride, freon series, organic ketone, amine, alcohol, ether, ester, acid and petroleum hydrocarbon compound etc.
The present invention has following useful effect:
1. the present invention utilizes graphene oxide to receiving the adsorption of micron catalyzer by TiO2Loading on graphene oxide sheet, the reaction between recycling amino and carboxyl will access on graphene oxide sheet containing N compound (Dopamine HCL and trimeric cyanamide), prepare matrix material. Relatively traditional TiO2Carbon composite, the material ratio surface-area that the present invention obtains is higher, and its BET specific surface area is 890-1250m2/ g is much larger than common TiO2And TiO2(their BET is about 500m for-G material2/ below g), there is microvoid structure (aperture < 1.7Kong Rong account for total hole hold volume ratio more than 60%); Degree of graphitization in pore structure more than 40%, higher than gac, the commercial sorbent material of activated carbon fiber.
2. the product obtained of the present invention has catalysis and absorption two kinds of functions, first by VOCs molecular oxidation, then can be adsorbed by weakly alkaline surface, has the selective adsorption that VOCs molecule is very high.
3. the present invention adopts nonpolar stronger poly-Dopamine HCL/trimeric cyanamide-Graphene porous charcoal to be carrier, greatly improves the nonpolar of adsorption site, weakens surface to the adsorption of water, plays hydrophobic effect. These features of material become the superior adsorbent of a class harmful VOCs molecule of efficient capture in wet environment. Such as in dry situation, the loading capacity of this material PARA FORMALDEHYDE PRILLS(91,95), acetaldehyde, benzene, toluene and dimethylbenzene far exceedes gac and adsorbent of molecular sieve, and the loading capacity of material PARA FORMALDEHYDE PRILLS(91,95), acetaldehyde, benzene, toluene and dimethylbenzene is also higher than materials such as SY-1, FE200 and MIO-199 under high humidity and lower concentration (60RH% and < 200ppm) condition.
4. H-TiO prepared by the present invention2N-G/C material can be used for the field such as catalysis and absorption.
Accompanying drawing explanation
Fig. 1 is the H-TiO obtained by embodiment 22The N of N-G/C material2Absorption/desorption isotherm.
Fig. 2 is the constituent content of embodiment 1-3.
Fig. 3 is the Raman spectrum figure of embodiment 3.
Fig. 4 be embodiment 2 under 298K, acetaldehyde is at obtained H-TiO2The adsorption isothermal line of N-G/C material.
Fig. 5 tri-kinds of materials compare with the loading capacity of PARA FORMALDEHYDE PRILLS(91,95) steam (200ppm) under relative humidity 55% condition dry.
The loading capacity of benzene, toluene and xylene steam (200ppm) is compared by Fig. 6 embodiment 3 under drying and relative humidity 55% condition.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
One, H-TiO2The preparation of N-G/C double-function catalyzing sorbing material.
Embodiment 1
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the ethanolic soln (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 2
Being added drop-wise in the aqueous solution containing 50mg graphene oxide by the ethylene glycol solution (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 15mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.375g trimeric cyanamide and 1.125g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 550 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Content is 18%, reacts 2h at 300 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 3
Being added drop-wise in the aqueous solution containing 0.5mg graphene oxide by the aqueous isopropanol (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 1.0mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.225g trimeric cyanamide and 1.53g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 700 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 10%, reacts 0.5h at 400 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 4
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the aqueous isopropanol (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 5
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the ethylene glycol solution (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 6
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the ethylene glycol/alcohol mixed solution (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 7
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the ethylene glycol/isopropyl alcohol mixture (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 8
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the ethanol/isopropyl alcohol mixture (5mL) containing 0.1mL butyl (tetra) titanate (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Embodiment 9
Being added drop-wise in the aqueous solution containing 100mg graphene oxide by the ethanol/Virahol containing 0.1mL butyl (tetra) titanate/ethylene glycol mixing solutions (5mL) (aqueous solution is 30mL), vigorous stirring generates without sizing TiO to fully hydrolysis2, obtained TiO2GO material; 0.417g trimeric cyanamide and 0.208g Dopamine HCL are dissolved into above-mentioned obtained TiO2Being polymerized in the solution of GO, after reaction, filtering drying obtains TiO2GO-composition polymer; By TiO2GO-composition polymer be placed in 400 DEG C at carbonization reaming, obtain TiO2N-G/C double-function catalyzing adsorption composite material; Finally by TiO2N-G/C is placed in H2/N2Atmosphere carries out reduction reaction, H2Volume content is 25%, reacts 4h at 200 DEG C, finally obtains H-TiO2N-G/C double-function catalyzing sorbing material.
Two, H-TiO2The physico-chemical property of N-G/C double-function catalyzing sorbing material, spectral data and structure are determined.
Adopt 2042 specific surface pore size distribution instrument of Micro company of U.S. production to the H-TiO prepared by the present invention2The pore texture of N-G/C measures. The S-3400N that Hitachi company of employing Japan produces and the LabRAMHR-800 that Horiba company of Japan produces is to the H-TiO prepared by the present invention2Constituent content and the degree of graphitization of N-G/C have characterized.
Fig. 1 and table 1 respectively illustrates the H-TiO obtained by embodiment 22The N of N-G/C material2The parameter information of absorption/desorption isotherm and three kinds of embodiment pore structures. As seen from Figure 1, N2 is had very big loading capacity at low pressure area (relative pressure < 0.1) by obtained material, and also have certain loading capacity at middle nip (0.1 < relative pressure < 0.5), it is seen that micro-multi-stage artery structure in the existence of this material. As shown in Table 1, the Langmuir specific surface area of all embodiment samples is at 890-1250m2/ g, total Kong Rong is about 0.30-0.49cm3Between/g, Micropore volume (aperture < 1.7) account for more than the 60% of total Kong Rong. Middle hole in material is mainly curling between graphene sheet layer to be formed. Middle hole in material is conducive to the diffusion of VOCs molecule in duct, and micropore provides the strong adsorption site to VOCs molecule. According to test result display, in embodiments of the invention coverage, prepare the H-TiO obtained2N-G/C material is a kind of loading type porous carbon material with high specific surface area.
The specific surface area of the Dopamine HCL of table 1. three kinds of embodiment gained/Graphene carbon composite and pore size distribution.
Smicro, Vt, and VmicroRepresent the specific surface area that micropore provides respectively, the Kong Rong that total Kong Rong and micropore provide.
Fig. 2 shows the element mass content of C, N, O and Ti of three kinds of embodiment samples. As can be seen from the figure, the carbon content in material more than 45%, leaded wastewater at 6-15%, with Ti at H-TiO2Content 15-27% in N-G/C material.
Fig. 3 shows the Raman spectrum figure of embodiment 3. As can be seen from the figure 1346 and 1587cm-1Position has two Raman peaks respectively, representative be defect and the degree of graphitization of material. According to peak area integration, we can obtain IG/IDIt is 0.75, shows that this material SP2 hydridization carbon content is higher.
Further, to the H-TiO prepared by other embodiments2N-G/C double-function catalyzing sorbing material carries out detection as hereinbefore, and its result is all identical, and circulation ratio is fabulous.
Three, H-TiO2The application of N-G/C double-function catalyzing sorbing material
The 3Flex adopting Micro company of the U.S. to produce measures acetaldehyde and has carried out Static Adsorption test in embodiment 2, adopts again the homemade closed system in laboratory (gas volume 500mL) that embodiment 3 has been carried out Static Adsorption test simultaneously.
Fig. 4 shows when 298K, the adsorption isothermal line of acetaldehyde on embodiment 2 material. As we know from the figure, the adsorption isothermal line of this material PARA FORMALDEHYDE PRILLS(91,95) presents typeI type, and before 10kP, the loading capacity of acetaldehyde presents the trend raised up rapidly, and this shows: material is stronger to the adsorption of acetaldehyde; In addition, the saturated adsorption capacity of acetaldehyde is also had advantage by material, about can reach 8.7mmol/g, obviously higher than common porous adsorbent, such as gac and molecular sieve.
Fig. 5 shows under 293K and dry and relative humidity 55% condition (concentration of formaldehyde is 200ppm), formaldehyde steam at embodiment 3 gained material and FE200 (ACF), the loading capacity on MOF-199 and N-G/C material. As can be seen from the figure, the loading capacity of embodiment 3 PARA FORMALDEHYDE PRILLS(91,95) steam under relative humidity 55% condition is the highest, Yue Keda 4.2mmol/g, is 3.2 and 35 times of FE200 and MIO-199 PARA FORMALDEHYDE PRILLS(91,95) loading capacity. Contrast is dry and high humidity two conditions, we this it appears that, the abundant sorbent material of oxy radical is in high humidity situation, and the loading capacity of its PARA FORMALDEHYDE PRILLS(91,95) relatively declines under drying conditions very big, and this mainly tries to be the first due to water molecules and occupies caused by adsorption potential; And N-G/C material is owing to having less oxy radical, FE200 and MOF-199 so the water resisting property in the wet situation of height to be better than, but water molecules is still had certain adsorption by the N group that its surface exists.
As a certain amount of reduction-state TiO of load on N-G/C composite porous charcoal2After, the competitive adsorption of water molecules on material has been got back enhancing by formaldehyde. Although due to TiO2Load may cause H-TiO2N-G/C material ratio surface-area has decline to a certain degree, but two mechanism of catalyzing cooperation absorption improve H-TiO2The loading capacity of N-G/C material PARA FORMALDEHYDE PRILLS(91,95) molecule at high humidity.
Fig. 6 shows under 293K and drying and relative humidity 55% condition (VOCs concentration is 200ppm), benzene, toluene and the xylene steam loading capacity on embodiment 3 gained material. As can be seen from the figure, embodiment 3 loading capacity to three kinds of benzene series thing steam under dry and relative humidity 55% condition is all higher. Illustrate that benzene series thing VOCs is also had higher capture ability by this material.
At H-TiO2The application aspect of N-G/C double-function catalyzing sorbing material, although the present invention just gives above-described embodiment, but from the experimental result of applicant, H-TiO2N-G/C double-function catalyzing sorbing material prepared by the present invention to described volatile organic matter VOCs, as alkane class, aromatic hydrocarbons, alkene class, halogen hydrocarbon class, ester class, aldehyde class, ketone class have identical effect. Especially to aldehyde class and benzene series thing particular significant effect. The main component of general volatile organic matter VOCs has: hydrocarbon class, halohydrocarbon, oxygen hydrocarbon and nitrogen hydrocarbon, and it comprises: organic chloride, freon series, organic ketone, amine, alcohol, ether, ester, acid and petroleum hydrocarbon compound etc.
In order to verify the characterization of adsorption under different states of the material prepared by the present invention more intuitively, it has been carried out relevant contrast experiment to similar close current material by applicant, and concrete outcome is such as table 2.
Material, SY-1 gac and the TiO that table 2 embodiment of the present invention 4 prepares2Graphene three kinds of materials are being done under wet condition the loading capacity of aldehyde class and benzene series thing VOCs molecule
Further, the material prepared by other embodiments is carried out same simultaneous test by applicant, and the display of experimental data result is basic and table 2 is identical. H-TiO prepared by the present invention as can be seen here2N-G/C double-function catalyzing sorbing material compared with similar close current material, equal dry when, the H-TiO prepared by the present invention2The adsorptive capacity of N-G/C double-function catalyzing sorbing material is obviously higher than the adsorptive capacity of similar close current material; H-TiO when relative humidity is higher, prepared by the present invention2The adsorptive capacity of N-G/C double-function catalyzing sorbing material is also obviously higher than the adsorptive capacity of similar close current material.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention. For those of ordinary skill in the field, other multi-form change or variations can also be done on the basis of the above description. Here without the need to also cannot all enforcement modes be given exhaustive. All any amendment, equivalent replacement and improvement etc. done within the spirit and principles in the present invention, all should be included within the protection domain of the claims in the present invention.
Claims (8)
1. a H-TiO2N-G/C double-function catalyzing sorbing material, it is characterised in that: described H-TiO2N-G/C double-function catalyzing sorbing material has microvoid structure, and described microvoid structure is primarily of content > the greying C of 45wt%, the N of content 6-15wt%, content > TiO of 25wt%2With the 3 D pore canal skeleton of a small amount of O and H element composition, described H-TiO2The BET specific surface area of N-G/C double-function catalyzing sorbing material is 890-1250m2/ g, described H-TiO2N-G/C double-function catalyzing sorbing material mesoporousMicropore volume account for total hole hold volume ratio 60%.
2. a H-TiO as claimed in claim 12The preparation method of N-G/C double-function catalyzing sorbing material, it is characterised in that: comprise the steps:
(1) butyl (tetra) titanate is dissolved in selective solvent, it is added drop-wise in the aqueous solution containing graphene oxide sheet, butyl (tetra) titanate hydrolysis is generated without sizing TiO2Colloidal sol, described nothing sizing TiO2The oxidized graphene film absorption of colloidal sol, obtains TiO2GO material; Described TiO2The structural unit of GO is:
I described in formula is graphene oxide sheet, and II is without sizing TiO2Colloidal sol;
(2) trimeric cyanamide and Dopamine HCL are dissolved into containing TiO2In the aqueous solution of GO material, the oxy radical on graphene oxide sheet surface is polymerized with the amino reaction on trimeric cyanamide TPA and Dopamine HCL PDA, preparation TiO2GO-TPA/PDA; Described TiO2The skeleton symbol of GO-TPA/PDA is:
The structural unit of the PDA described in formula is:
The structural unit of the TPA described in formula is:
(3) by TiO2GO-TPA/PDA puts into N2The tubular react furnace of atmosphere carries out high-temperature calcination, obtained TiO2N-G/C composite porous charcoal; TiO simultaneously2Make the transition from without sizing to anatase octahedrite, described TiO2The skeleton symbol of N-G/C composite porous charcoal is:
In formula, III is Detitanium-ore-type TiO2, IV is the compound porous carbon of N-G/C;
(4) by TiO2N-G/C is placed in, at H2/N2Atmosphere carries out reduction reaction, the TiO on composite porous charcoal2It is reduced and generates H-TiO2, finally obtain H-TiO2N-G/C double-function catalyzing sorbing material.
3. H-TiO according to claim 22The preparation method of N-G/C double-function catalyzing sorbing material, it is characterised in that: the mass ratio of the trimeric cyanamide described in step (2) and Dopamine HCL is 1:(0.5��6); Described trimeric cyanamide and TiO2The mass ratio of GO is 1:(0.1��0.3).
4. H-TiO according to claim 22The preparation method of N-G/C double-function catalyzing sorbing material, it is characterised in that: calcining temperature described in step (3) is 400��700 DEG C.
5. according to the arbitrary described H-TiO of claim 2-42The preparation method of N-G/C double-function catalyzing sorbing material, it is characterized in that: the mass ratio of the butyl (tetra) titanate described in step (1) and graphene oxide is 1:(0.05��1), the mixed volume of selective solvent and water is than being 1:(0.2��6); The mixing of the one or more than one that described selective solvent is selected from ethanol, ethylene glycol, Virahol.
6. H-TiO according to claim 52The preparation method of N-G/C double-function catalyzing sorbing material, it is characterised in that: the reducing atmosphere component H described in step (4)2/N2Volume ratio is in 1:(3��9), temperature of reaction is at 200��400 DEG C, and the reaction times is at 0.5��4h.
7. a H-TiO as claimed in claim 12The application of N-G/C double-function catalyzing sorbing material, it is characterised in that: described H-TiO2N-G/C double-function catalyzing sorbing material is applied to the catalysis to volatile organic matter VOCs and absorption.
8. H-TiO according to claim 72The application of N-G/C double-function catalyzing sorbing material, it is characterised in that: described H-TiO2N-G/C double-function catalyzing sorbing material is applied in wet environment to the catalysis of volatile organic matter VOCs and absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118641.6A CN105617991B (en) | 2016-03-03 | 2016-03-03 | A kind of H-TiO2@N-G/C double-function catalyzing sorbing materials and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118641.6A CN105617991B (en) | 2016-03-03 | 2016-03-03 | A kind of H-TiO2@N-G/C double-function catalyzing sorbing materials and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105617991A true CN105617991A (en) | 2016-06-01 |
| CN105617991B CN105617991B (en) | 2018-08-14 |
Family
ID=56033564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610118641.6A Active CN105617991B (en) | 2016-03-03 | 2016-03-03 | A kind of H-TiO2@N-G/C double-function catalyzing sorbing materials and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105617991B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887580A (en) * | 2017-04-27 | 2017-06-23 | 中南大学 | A kind of lithium ion battery negative material and preparation method thereof |
| CN108927112A (en) * | 2018-09-21 | 2018-12-04 | 佛山皖和新能源科技有限公司 | A kind of graphene composite aerogel adsorbent |
| CN113948691A (en) * | 2021-10-15 | 2022-01-18 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803291A (en) * | 2006-01-20 | 2006-07-19 | 中国科学院广州地球化学研究所 | Titanium dioxide/active carbon fiber photocatalyst and its preparation method and uses in air purification |
| JP2007260603A (en) * | 2006-03-29 | 2007-10-11 | Suminoe Textile Co Ltd | Filter unit for air cleaner |
| CN101318129A (en) * | 2008-07-23 | 2008-12-10 | 刘守新 | Supported optical catalyst and preparation method thereof |
| CN105032388A (en) * | 2015-07-21 | 2015-11-11 | 河北科技大学 | Sludge activated carbon-loaded TiO2 complex photocatalyst and application thereof |
| CN105080529A (en) * | 2014-05-13 | 2015-11-25 | 江苏瑞丰科技实业有限公司 | Normal temperature catalytic material for efficiently removing VOCs |
-
2016
- 2016-03-03 CN CN201610118641.6A patent/CN105617991B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803291A (en) * | 2006-01-20 | 2006-07-19 | 中国科学院广州地球化学研究所 | Titanium dioxide/active carbon fiber photocatalyst and its preparation method and uses in air purification |
| JP2007260603A (en) * | 2006-03-29 | 2007-10-11 | Suminoe Textile Co Ltd | Filter unit for air cleaner |
| CN101318129A (en) * | 2008-07-23 | 2008-12-10 | 刘守新 | Supported optical catalyst and preparation method thereof |
| CN105080529A (en) * | 2014-05-13 | 2015-11-25 | 江苏瑞丰科技实业有限公司 | Normal temperature catalytic material for efficiently removing VOCs |
| CN105032388A (en) * | 2015-07-21 | 2015-11-11 | 河北科技大学 | Sludge activated carbon-loaded TiO2 complex photocatalyst and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YANHUI ZHANG ET AL.: "TiO2-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant:is TiO2-graphene truly different from other TiO2-carbon composite materials?", 《ACS NANO》 * |
| 卢辛成等: "挥发性有机物的治理以及活性炭的应用研究进展", 《生物质化学工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887580A (en) * | 2017-04-27 | 2017-06-23 | 中南大学 | A kind of lithium ion battery negative material and preparation method thereof |
| CN108927112A (en) * | 2018-09-21 | 2018-12-04 | 佛山皖和新能源科技有限公司 | A kind of graphene composite aerogel adsorbent |
| CN113948691A (en) * | 2021-10-15 | 2022-01-18 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
| CN113948691B (en) * | 2021-10-15 | 2023-03-10 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105617991B (en) | 2018-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| To et al. | Hierarchical N-doped carbon as CO2 adsorbent with high CO2 selectivity from rationally designed polypyrrole precursor | |
| Gan et al. | Carbon aerogels for environmental clean‐up | |
| Chowdhury et al. | Three-dimensional graphene-based porous adsorbents for postcombustion CO2 capture | |
| Yu et al. | Magnetic iron oxide nanoparticles functionalized multi-walled carbon nanotubes for toluene, ethylbenzene and xylene removal from aqueous solution | |
| Joung et al. | Catalytic oxidation of VOCs over CNT-supported platinum nanoparticles | |
| Gangupomu et al. | Comparative study of carbon nanotubes and granular activated carbon: physicochemical properties and adsorption capacities | |
| Zhao et al. | VOC removal: comparison of MCM-41 with hydrophobic zeolites and activated carbon | |
| Ding et al. | A new insight into catalytic ozonation with nanosized Ce–Ti oxides for NO x removal: Confirmation of Ce–O–Ti for active sites | |
| Qiu et al. | Cerium‐based metal–organic frameworks with UiO architecture for visible light‐induced aerobic oxidation of benzyl alcohol | |
| Xu et al. | Microemulsion‐Assisted Preparation of a Mesoporous Ferrihydrite/SiO2 Composite for the Efficient Removal of Formaldehyde from Air | |
| Shi et al. | Adsorptive desulfurization performances of ordered mesoporous carbons with tailored textural and surface properties | |
| Toprak et al. | Carbon dioxide adsorption using high surface area activated carbons from local coals modified by KOH, NaOH and ZnCl2 agents | |
| Zhang et al. | Effect of Promotion with Ru Addition on the Activity and SO2 Resistance of MnO x–TiO2 Adsorbent for Hg0 Removal | |
| Deng et al. | New type nitrogen-doped carbon material applied to deep adsorption desulfurization | |
| Zhao et al. | A Facile Approach to Fabricate an N‐Doped Mesoporous Graphene/Nanodiamond Hybrid Nanocomposite with Synergistically Enhanced Catalysis | |
| Yuan et al. | Glow discharge plasma-assisted template removal of SBA-15 at ambient temperature for high surface area, high silanol density, and enhanced CO2 adsorption capacity | |
| Bobb et al. | Laser synthesis of carbonaceous TiO2 from metal–organic frameworks: optimum support for Pd nanoparticles for C–C cross-coupling reactions | |
| CN105617991A (en) | H-TiO2@N-G/C dual-functional catalytic adsorption material and preparation method and application thereof | |
| Przepiórski et al. | MgO/CaO-loaded activated carbon for carbon dioxide capture: practical aspects of use | |
| Ion et al. | Volatile organic compounds adsorption onto neat and hybrid bacterial cellulose | |
| Huang et al. | Hydrogen from Water over Openly‐Structured Graphitic Carbon Nitride Polymer through Photocatalysis | |
| Wang et al. | Resin‐Derived Hierarchical Porous Carbon Spheres with High Catalytic Performance in the Oxidative Dehydrogenation of Ethylbenzene | |
| Zhang et al. | Hierarchical titanium dioxide nanowire/metal–organic framework/carbon nanofiber membranes for highly efficient photocatalytic degradation of hydrogen sulfide | |
| Zuo et al. | Efficient and environmentally friendly synthesis of AlFe-PILC-supported MnCe catalysts for benzene combustion | |
| Chen et al. | Sustainable recovery of gaseous mercury by adsorption and electrothermal desorption using activated carbon fiber cloth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |