CN106824065A - The graphene-based TiO of humic acid in a kind of removal rural potable water2Nano composite material and preparation method thereof - Google Patents
The graphene-based TiO of humic acid in a kind of removal rural potable water2Nano composite material and preparation method thereof Download PDFInfo
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- CN106824065A CN106824065A CN201611245766.1A CN201611245766A CN106824065A CN 106824065 A CN106824065 A CN 106824065A CN 201611245766 A CN201611245766 A CN 201611245766A CN 106824065 A CN106824065 A CN 106824065A
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- graphene
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- nano composite
- humic acid
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000004021 humic acid Substances 0.000 title claims abstract description 43
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 claims abstract description 44
- 239000003651 drinking water Substances 0.000 claims abstract description 23
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000004317 sodium nitrate Substances 0.000 claims description 13
- 235000010344 sodium nitrate Nutrition 0.000 claims description 13
- 235000012206 bottled water Nutrition 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 230000002308 calcification Effects 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 235000020188 drinking water Nutrition 0.000 abstract description 8
- 239000005416 organic matter Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 230000010512 thermal transition Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000010936 titanium Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical class [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 101150064138 MAP1 gene Proteins 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001795 light effect Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 208000020084 Bone disease Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241001125671 Eretmochelys imbricata Species 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000012675 alcoholic extract Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- -1 polycyclic Aromatic compound Chemical class 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000000108 ultra-filtration 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
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of graphene-based TiO for removing humic acid in rural potable water2Nano composite material and preparation method thereof.With ammonium titanium fluoride as raw material, graphene oxide and ammonium titanium fluoride are mixed into water-filling thermal transition to the preparation method by the graphene oxide prepared with hummers methods as carrier, then by hydro-thermal method, prepare the graphene-based TiO2Nano composite material.Preparation method preparation process is simple of the present invention, is not required to expensive device, and raw material is easy to get, environmental protection, and with low cost, cost performance is high, preparation process non-environmental-pollution；Graphene-based TiO of the invention2Nano composite material, with larger specific surface area, can adsorb more organic matter; using process non-environmental-pollution; removal efficiency to organic matter is high, is that drinking water safety and environment water protection are provided and provided powerful support for, and can be widely used in humic acid in actual removal drinking water.
Description
Technical field
The present invention relates to photocatalysis adsorption technology field, and in particular to the light with humic acid in efficiently removal drinking water is urged
Change adsorption composite material and preparation method thereof.
Background technology
Humic acid is the important natural extinction material being widely present in surface water and soil, is natural organic matter in water body
Main component（Account for the 50%~90% of total organic matter）, the macromolecular of various functional groups such as phenolic hydroxy group, carboxyl, alcoholic extract hydroxyl group is polycyclic
Aromatic compound, is one of Main Ingredients and Appearance of colourity in composition water body.Have between heavy metal ion in humic acid molecule and water compared with
Strong complexing, can strengthen the stability of colloid, can form combined pollutant, so as to influence water treatment efficiency；Drinking
In water process, humic acid material can generate the chlorine disinfection by-products such as chloroform (THMs), halogen acetic acid (HAAs) with chlorine reaction
(DBPs) main predecessor, belongs to teratogenesis carcinogenic substance；Humic acid can influence absorption and metabolic balance of the human body to inorganic elements,
Cause the generation of big osteopathy, therefore, the presence of humic acid can directly threaten the health of the mankind in water body.Chelating, absorption and oxidation
Reducing power, to organic and inorganic compound nature migration, conversion and home to return to, drinking water source area water quality have very weigh
The influence wanted, therefore for how to remove humic acid in drinking water source area water body, it has also become environment circle grinds economical and efficient
Study carefully focus.
At present, humic acid research mainly has membrane filter technique, flocculence, oxidizing process, life using more method in removal water body
Thing method, absorption method etc., but all be there are problems that in actual application.Although membrane filter technique can remove macromolecular complex
Matter, is but very difficult to except hydrophilic small molecules organic matter；Humic acid is the difficult anionic macromolecular and hydrophilic and hydrophobic group decomposed
Point, charge etc. directly affect the reduction of clearance and flux in ultra-filtration process, easily cause fouling membrane.Flocculence can be effective
The DBPs of ground removal colloidal type, humic acids and high score subclass（DBPs）Precursor, and to deliquescent non-humic acids
And low molecule（DBPs）The removal effect of precursor is relatively poor.Although flocculence is one kind to be not required to increase enormous investment and can realize
The important technology of DBPs formation is controlled on existing treatment structure base, but it is often difficult to effectively remove solubilised state
DBPs precursors, so that the water outlet after coagulating treatment does not reach requirement, increase the treatment load of subsequent handling, to drinking water
Safety constitutes potential threat.Biological rule will cultivate corresponding microorganism and carry out biodegradation, to waterpower in processing procedure
The requirement of load, p H values, temperature and aeration rate is higher, while its clearance is relatively low；Although Ozonation can be with bactericidal purifying water
Matter, but ozone needs scene to occur, and operating cost is higher.
Photocatalysis oxidation technique is to study relatively broad method for treating water over nearly 20 years.Titanium dioxide is due to its uniqueness
Photocatalysis characteristic, the environmental type catalyst for most having exploitation future as a new generation is dirty in water environment purified treatment, air
The focus that dye is administered, has a wide range of applications in anti-biotic material and turn into research.Since Carey in 1976 proposes Polychlorinated biphenyls
Can be in TiO2Since the lower photocatalysis Decomposition of/UV effects, many people have carried out multinomial photocatalytic-oxidation to the organic pollution in water
Change and decompose research.There are some researches show under ultraviolet light, TiO2Produce the OH and O of strong oxidizing property2-Free radical, with humic
There is radical chain reaction in acid, humic acid is changed into small molecule or even carbon dioxide, water and inorganic acid.But, due to
TiO2Energy gap wider causes to absorb the limited in one's ability of visible ray, recycles and reuses difficulty.Therefore, to photochemical catalyst
Modified to prepare, so as to obtain, absorbing ability is strong, and the good catalyst of recycling performance is asked as research the important of photochemical catalyst
Topic.
Graphene is a kind of carbon atomic layer of the monoatomic thickness of two-dimensional structure, is the most thin material having now been found that, by
The two dimensional crystal material of single layer of carbon atom composition, perfect graphene-structured is the six-membered ring structure of carbon atom, and is periodically arranged
Be listed in the dilute plane of graphite, wherein each carbon atom with three adjacent carbon atoms with sp2The mode of hydridization is mutually bonded, each
Carbon atom contributes a pi-electron for non-bonding to constitute π tracks again, and pi-electron can be moved freely, and assign Graphene excellent
Conductive capability, the movement velocity of its electronics reaches the 1/300 of the light velocity.The thickness of Graphene is only 1 thickness of carbon atom, i.e.,
The bond distance of 0.335nm, C-C key be 0.142 nm, 120 ° of bond angle, it be constitute other dimension carbon materials elementary cell.Stone
Black alkene has advantages below：（1）Graphene has good electronic transmission performance.Graphene is valence band（Pi-electron）And conduction band
（π * electronics）The zero gap semiconductor material of any is met at, the carrier in Graphene can be that electronics can also be hole.Stone
The electric charge carrier of black alkene can be continuously adjusted between electronics and hole, and carrier mobility speed hardly receives temperature shadow
Ring, mobility very high can be obtained at room temperature, if ignoring the influence of impurity, its theoretical migration rate is up to 2 × 105
cm2/V•S.（2）Graphene has high hardness and intensity on mechanics, is mechanical strength highest material so far.
（3）Graphene has thermal conductivity higher.（4）The specific surface area theoretical value of Graphene is up to 2600m2/ g, to near-infrared, can
See that light and ultraviolet light are respectively provided with excellent permeability, it is far above other carbon materials, meanwhile, Graphene also has potential magnetic
Energy.Graphene also has many unique physical properties such as quantum hall effect at room temperature, quantum tunneling effect.Graphene
These advantages make it be widely used in fields such as electronic technology, energy storages.
To improve TiO2Light absorpting ability, with reference to the good characteristic of Graphene, by the regulation of experiment condition, in graphite
Graphene-nano titania composite catalyzing particle is realized on alkene carrier, by TiO2It is combined with each other with Graphene.Due to graphite
The special electronic structure of alkene, by Graphene and TiO2The composite photo-catalyst removal humic acid of synthesis, tool has great advantage：
（1）In light-catalyzed reaction system, due to Graphene and nano-TiO2Unique texture, Graphene-TiO2Nano composite material energy
Enough surfaces that substantial amounts of humic acid in solution is adsorbed onto composite, with adsorption activity high, quickly reach adsorption equilibrium；
（2）Ultraviolet light effect induction TiO2Light induced electron produced by inside is obtained effectively with hole through the moditied processing of Graphene
Separation, effectively inhibit TiO2Light induced electron and photohole it is compound, quantum efficiency is improved obviously, light induced electron
Further reaction generates various active materials respectively with hole, and subsequent oxidative degradation absorption is in Graphene-TiO2Nano combined material
The humic acid on surface is expected, finally because ultraviolet light effect is by photocatalytic degradation.
Therefore, based on two kinds of effect synergies of adsorption-photocatalytic degradation, Graphene-TiO2Nano composite material is showed
Enhanced photocatalytic activity is gone out, has made TiO2Combination property preferably bring into play, enhance Graphene-TiO2Nanostructured
Efficiency of the compound in adsorption-photocatalytic degradation Organic Pollutants In Water.
The content of the invention
It is an object of the invention to provide a kind of graphene-based TiO with efficiently removal humic acid2Nano composite material,
The material is adsorbed and high catalytic efficiency, for the removal of the humic acid in water body provides a kind of new way efficiently, inexpensive, energy
It is advantageously applied to the removal of humic acid in rural potable water.
The present invention also provides a kind of graphene-based TiO2The preparation method of nano composite material.The method is with fluotitanic acid
Ammonium is raw material, the graphene oxide prepared with hummers methods as carrier, then by hydro-thermal method by graphene oxide and fluotitanic acid
Ammonium is mixed into water-filling thermal transition, prepares the graphene-based TiO2Nano composite material；Obtained graphene-based TiO2Nanometer
TiO in composite2It is Detitanium-ore-type.
The object of the invention is achieved through the following technical solutions.
The graphene-based TiO of humic acid in a kind of removal rural potable water2The preparation method of nano composite material, including such as
Lower step：
（1）In ice-water bath, by the sodium nitrate addition concentrated sulfuric acid, stirring to sodium nitrate powder suspends in the solution, adds graphite powder,
Continue to stir, obtain mixed solution；Potassium permanganate is added in the mixed solution for obtaining, stirring is extremely formed under water bath condition
Underflow；
（2）Deionized water dilution is slowly added in the underflow for obtaining, is stirred, heated up, deionized water dilution is added again
Above-mentioned underflow, is slowly added to hydrogen peroxide, continues stirring and obtains mixed solution；By mixed solution centrifugation, supernatant is removed, sunk
Starch uses hydrochloric acid and deionized water centrifuge washing successively；By the sediment after washing in ultrasonic disperse in water, stablized
Graphene oxide solution；
（3）Ammonium titanium fluoride and boric acid are added in graphene oxide solution, is stirred, heating is closed under water bath condition；Heating
After end, mixed liquor is filtered, washing precipitate, dried；Dried solid is heated into calcification processing in Muffle furnace, is obtained
The graphene-based TiO2Nano composite material.
Further, step（1）In, the concentrated sulfuric acid is 46 with the liquid ratio of sodium nitrate:1 ml/g.
Further, step（1）In, the graphite powder is 1 with the mass ratio of sodium nitrate:1.
Further, step（1）In, after sodium nitrate is added into the concentrated sulfuric acid, the time of stirring is 0.5 ~ 2h.
Further, step（1）In, the time for continuing to stir is 1h.
Further, step（1）In, the potassium permanganate is 6 with the mass ratio of graphite powder:1.
Further, step（1）In, stirring is to stir 1h under 35 DEG C of water bath conditions under the water bath condition.
Further, step（2）In, the volume ratio that deionized water is added for the first time and for the second time is 2:5.
Further, step（2）In, the mixing time after adding deionized water in underflow is 30min.
Further, step（2）In, the intensification is to be warming up to temperature for 90 DEG C.
Further, step（2）In, the mass concentration of the hydrogen peroxide is 30%, and the addition of hydrogen peroxide is gone with for the second time
The volume ratio of ionized water addition is 3:100.
Further, step（2）In, after adding hydrogen peroxide, the time for continuing to stir is 30min.
Further, step（2）In, the mass concentration of the hydrochloric acid is 3%.
Further, step（2）In, the washing is to wash the pH value to cleaning solution 6 ~ 7.
Further, step（2）In, the time of the ultrasonic disperse is 1h.
Further, step（3）In, the mass ratio of the graphene oxide in the ammonium titanium fluoride and graphene oxide solution
It is 8 ~ 12:1.
Further, step（3）In, the ammonium titanium fluoride is 5 with the mass ratio of boric acid:4~6.
Further, step（3）In, the temperature of heating is closed under the water bath condition for 60 DEG C, the time is 2h.
Further, step（3）In, the dry temperature is 60 DEG C, and the time is 10 ~ 24h.
Further, step（3）In, it is described heating calcification processing temperature be 200 ~ 500 DEG C, preferably 200 ~ 500 DEG C,
Time is 1h.
Humic acid is graphene-based in a kind of removal rural potable water obtained in the preparation method as described in any of the above-described
TiO2Nano composite material.
Compared with prior art, the invention has the advantages that and beneficial effect：
（1）Preparation method preparation process is simple of the present invention, is not required to expensive device, and raw material is easy to get, environmental protection, with low cost, cost performance
Height, preparation process non-environmental-pollution；
（2）Graphene-based TiO of the invention2Nano composite material, with larger specific surface area, can adsorb more organic
Thing, is using process non-environmental-pollution, and the removal efficiency to organic matter is high, is that drinking water safety and environment water protection are provided with
Power support, can be widely used in the removal of humic acid in actual drinking water.
Brief description of the drawings
Fig. 1 is graphene-based TiO prepared by embodiment 12The transmission electron microscope of nano composite material（TEM）Figure；
Fig. 2 is graphene-based TiO prepared by embodiment 12The high-resolution x-ray photoelectron of nano composite material（XPS）Energy spectrum diagram；
Fig. 3 is graphene-based TiO prepared by embodiment 12Humic acid is removed under the conditions of nano composite material difference dosage is imitated
The impact effect figure of rate.
Specific embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described, but the invention is not restricted to following examples.
Embodiment 1
Prepare a kind of graphene-based TiO for removing humic acid in rural potable water2Nano composite material, comprises the following steps：
（1）Round bottom beaker is placed in ice-water bath, the 23ml ice concentrated sulfuric acids are added, and adds 0.5g sodium nitrate, stirring 0.5h to nitre
Sour sodium powder end suspends in the solution；0.5g graphite powders, continuing magnetic force stirring 1h is added to obtain mixed solution；
（2）In step（1）3g potassium permanganate is slowly added in the mixed solution for obtaining, 1h, shape are stirred under 35 DEG C of water bath conditions
Into underflow；40mL deionized waters are slowly added to, agitating solution 30min, temperature is raised to 90 DEG C；100mL deionized waters are added, slowly
3mL 30wt% hydrogen peroxide is added, after stirring 30min；Mixed solution centrifugation, removes supernatant, is added in centrifuge tube
The hydrochloric acid solution and deionized water centrifuge washing of 3wt%, untill the pH of filtrate is for 6~7, obtain the aqueous solution of graphite oxide；
（3）Graphite oxide is scattered in the aqueous solution, 1 h is disperseed under ultrasound condition, the dispersion liquid stablized as is aoxidized
Graphene solution；
（4）Add 5g ammonium titanium fluorides and 6g boric acid, stirs uniform in graphene oxide solution, by solution in 60 DEG C of water-baths
Closing heating 2h；Filtering, washing precipitate, 60 DEG C of vacuum drying 10h, finally by dry solid 200 DEG C in Muffle furnace, plus
Hot 1h, obtains graphene-based TiO2Nano composite material.
Obtained graphene-based TiO2The SEM figures of nano composite material as shown in figure 1, as shown in Figure 1, in graphene-structured
In, it is dispersed with TiO2Particle, and TiO2Particle not simply mixes with Graphene, and is built-in the layer structure of Graphene
Among.Hydro-thermal process causes Graphene not single layer structure, but the uneven texture with MULTILAYER COMPOSITE that folds, and TiO2Particle
Grown along these pleated structures, so as to be distributed on the sandwich construction of Graphene.
Obtained graphene-based TiO2The xps energy spectrum figure of nano composite material is graphene-based as shown in Fig. 2 as shown in Figure 2
TiO2Nano composite material surface-element is mainly tetra- kinds of elements of Ti, O, C, F.
Graphene oxide only contains C, O element, except occurring in that symmetrical sp in 284.77 eV2The C-C of hydridization
Outside peak, also there is substantial amounts of epoxy radicals C-O（286.67 eV）With carboxyl O-C=O（289.02 eV）Deng oxygen-content active group.
In composite, except symmetrical sp2Outside the C-C peaks of hydridization are still present, other active groups include ring
The peak intensity of epoxide etc. drastically declines, and 283.91 eV positions occur in that in C 1s XPS spectrograms in composite
One peak；Because Graphene is used as carbon material, in preparation process, a small amount of carbon atom enters TiO2The lattice of anatase
In, generation bonds together to form C-Ti keys.
In composite in Ti 2p electron binding energies spectrum, Ti 2p3/2Combination can be 459.37e V, and elemental standards
Pure TiO in photoelectron spectroscopy2Middle Ti 2p3/2Electronics close can be 458.3 e V；With pure TiO2Compare, it is obtained nano combined
Ti 2p in material3/2Electron binding energy increased, illustrate Ti atoms in nano composite material chemical bonding state and
Pure TiO2In difference.
The graphene-based TiO for preparing2Influence under the conditions of nano composite material difference dosage to humic acid removal efficiency
Design sketch as shown in figure 3, from the figure 3, it may be seen that before 30min, graphene-based TiO2Nano composite material is right under dark condition
The Adsorption effect of humic acid has just reached 46.5%~59%；After 30min, graphene-based TiO under the irradiation of ultraviolet light2
Absorption-photocatalysis of the nano composite material to humic acid, humic acid removal effect can reach 74%~88.9%.Illustrate to inhale
Attached-two kinds of photocatalytic degradation effect synergy, graphene-based TiO2Nano composite material shows enhanced photocatalysis and lives
Property.
Embodiment 2
（1）Round bottom beaker is placed in ice-water bath, the 23ml ice concentrated sulfuric acids are added, and adds 0.5g sodium nitrate, stirring 1h to nitric acid
Sodium powder end suspends in the solution；0.5g graphite powders, continuing magnetic force stirring 1h is added to obtain mixed solution；
（2）In step（1）3g potassium permanganate is slowly added in the mixed solution for obtaining, 1h, shape are stirred under 35 DEG C of water bath conditions
Into underflow；40mL deionized waters are slowly added to, agitating solution 30min, temperature is raised to 90 DEG C；100mL deionized waters are added, slowly
3mL 30wt% hydrogen peroxide is added, after stirring 30min；Mixed solution centrifugation, removes supernatant, is added in centrifuge tube
The hydrochloric acid solution and deionized water centrifuge washing of 3wt%, untill the pH of filtrate is for 6~7, obtain the aqueous solution of graphite oxide；
（3）Graphite oxide is scattered in the aqueous solution, 1 h is disperseed under ultrasound condition, the dispersion liquid stablized as is aoxidized
Graphene solution；
（4）Add 5g ammonium titanium fluorides and 5.5g boric acid, stirs uniform in graphene oxide solution, by solution in 60 DEG C of water-baths
Middle closing heating 2h；Filtering, washing precipitate, 60 DEG C of vacuum drying 24h, finally by dry solid 300 DEG C in Muffle furnace,
Heating 1h, obtains graphene-based TiO2Nano composite material.
Obtained graphene-based TiO2The SEM situations Parameter Map 1, TiO of nano composite material2Particle is embedded in Graphene
Among layer structure, analyzed by xps energy spectrum, graphene-based TiO2Nano composite material surface-element is mainly Ti, O, C, F
Four kinds of elements；And obtained graphene-based TiO2Nano composite material is high to humic acid removal efficiency, shows enhanced light and urges
Change activity.
Embodiment 3
（1）Round bottom beaker is placed in ice-water bath, the 23ml ice concentrated sulfuric acids are added, and adds 0.5g sodium nitrate, stirring 2h to nitric acid
Sodium powder end suspends in the solution；0.5g graphite powders, continuing magnetic force stirring 1h is added to obtain mixed solution；
（2）In step（1）3g potassium permanganate is slowly added in the mixed solution for obtaining, 1h, shape are stirred under 35 DEG C of water bath conditions
Into underflow；40mL deionized waters are slowly added to, agitating solution 30min, temperature is raised to 90 DEG C；100mL deionized waters are added, slowly
3mL 30wt% hydrogen peroxide is added, after stirring 30min；Mixed solution centrifugation, removes supernatant, is added in centrifuge tube
The hydrochloric acid solution and deionized water centrifuge washing of 3wt%, untill the pH of filtrate is for 6~7, obtain the aqueous solution of graphite oxide；
（3）Graphite oxide is scattered in the aqueous solution, 1 h is disperseed under ultrasound condition, the dispersion liquid stablized as is aoxidized
Graphene solution；
（4）Add 5g ammonium titanium fluorides and 6g boric acid, stirs uniform in graphene oxide solution, by solution in 60 DEG C of water-baths
Closing heating 2h；Filtering, washing precipitate, 60 DEG C of vacuum drying 20h, finally by dry solid 400 DEG C in Muffle furnace, plus
Hot 1h, obtains graphene-based TiO2Nano composite material.
Obtained graphene-based TiO2The SEM situations Parameter Map 1, TiO of nano composite material2Particle is embedded in Graphene
Among layer structure, analyzed by xps energy spectrum, graphene-based TiO2Nano composite material surface-element is mainly Ti, O, C, F
Four kinds of elements；And obtained graphene-based TiO2Nano composite material is high to humic acid removal efficiency, shows enhanced light and urges
Change activity.
Claims (10)
1. it is a kind of remove rural potable water in humic acid graphene-based TiO2The preparation method of nano composite material, its feature exists
In comprising the following steps：
（1）In ice-water bath, by the sodium nitrate addition concentrated sulfuric acid, stirring to sodium nitrate powder suspends in the solution, adds graphite powder,
Continue to stir, obtain mixed solution；Potassium permanganate is added in the mixed solution for obtaining, stirring is extremely formed under water bath condition
Underflow；
（2）Deionized water dilution is slowly added in the underflow for obtaining, is stirred, heated up, deionized water dilution is added again
Above-mentioned underflow, is slowly added to hydrogen peroxide, continues stirring and obtains mixed solution；By mixed solution centrifugation, supernatant is removed, sunk
Starch uses hydrochloric acid and deionized water centrifuge washing successively；By the sediment after washing in ultrasonic disperse in water, stablized
Graphene oxide solution；
（3）Ammonium titanium fluoride and boric acid are added in graphene oxide solution, is stirred, heating is closed under water bath condition；Heating
After end, mixed liquor is filtered, washing precipitate, dried；Dried solid is heated into calcification processing in Muffle furnace, is obtained
The graphene-based TiO2Nano composite material.
2. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（1）In, the concentrated sulfuric acid is 46 with the liquid ratio of sodium nitrate:1 ml/g；The stone
Ink powder is 1 with the mass ratio of sodium nitrate:1；After sodium nitrate is added into the concentrated sulfuric acid, the time of stirring is 0.5 ~ 2h；The continuation
The time of stirring is 1h.
3. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（1）In, the potassium permanganate is 6 with the mass ratio of graphite powder:1；The water-bath bar
Stirring is to stir 1h under 35 DEG C of water bath conditions under part.
4. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（2）In, the volume ratio that deionized water is added for the first time and for the second time is 2:5.
5. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（2）In, the mixing time after adding deionized water in underflow is 30min；It is described
Intensification is to be warming up to temperature for 90 DEG C.
6. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（2）In, the mass concentration of the hydrogen peroxide is 30%, the addition of hydrogen peroxide and the
The volume ratio of secondary deionized water addition is 3:100；After adding hydrogen peroxide, the time for continuing to stir is 30min.
7. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（2）In, the mass concentration of the hydrochloric acid is 3%；The washing is washing to cleaning solution
PH value 6 ~ 7；The time of the ultrasonic disperse is 1h.
8. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（3）In, graphene oxide in the ammonium titanium fluoride and graphene oxide solution
Mass ratio is 8 ~ 12:1；The ammonium titanium fluoride is 5 with the mass ratio of boric acid:4~6.
9. it is according to claim 1 it is a kind of remove rural potable water in humic acid graphene-based TiO2Nano composite material
Preparation method, it is characterised in that step（3）In, the temperature of heating is closed under the water bath condition for 60 DEG C, the time is 2h；
The dry temperature is 60 DEG C, and the time is 10 ~ 24h；The temperature of the heating calcification processing is 200 ~ 500 DEG C, and the time is 1h.
10. obtained in the preparation method as described in any one of claim 1 ~ 9 it is a kind of remove rural potable water in humic acid graphite
Alkenyl TiO2Nano composite material.
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| CN115368766B (en) * | 2022-08-19 | 2023-11-07 | 佛山科学技术学院 | Fluorinated graphene/titanium dioxide composite anti-corrosion filler and preparation method thereof |
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