WO2016197397A1 - Preparation method and use of photocatalytic degradation-adsorption material - Google Patents
Preparation method and use of photocatalytic degradation-adsorption material Download PDFInfo
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- WO2016197397A1 WO2016197397A1 PCT/CN2015/081412 CN2015081412W WO2016197397A1 WO 2016197397 A1 WO2016197397 A1 WO 2016197397A1 CN 2015081412 W CN2015081412 W CN 2015081412W WO 2016197397 A1 WO2016197397 A1 WO 2016197397A1
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- photocatalytic degradation
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006260 foam Substances 0.000 claims abstract description 26
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- OXKUGIFNIUUKAW-UHFFFAOYSA-N n,n-dimethylformamide;hydrazine Chemical compound NN.CN(C)C=O OXKUGIFNIUUKAW-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 26
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005543 nano-size silicon particle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000009395 genetic defect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000008208 nanofoam Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/283—Porous sorbents based on silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
Definitions
- the invention belongs to the technical field of polymer nano composite materials, and particularly relates to an intelligent photocatalytic degradation-adsorption material preparation method and application thereof to chromium ion adsorption degradation.
- Chromium (Cr) is one of the most common heavy metals. It is widely found in natural environments. Chromium in water environment mainly comes from electroplating, smelting, tanning, textile, printing and dyeing, cement, steel, paint, pharmaceutical, etc. up to 80 Industrial wastewater discharge. Chromium in water usually exists in the form of hexavalent and trivalent forms. A small amount of trivalent chromium is essential for the human body.
- Spiropymn and its derivatives are currently widely studied as a kind of compound, which can realize the ring/closed loop transition under ultraviolet/visible illumination.
- the photoisomers can bind to metal ions, and thus spiropyrans and their derivatives have attracted the attention of many researchers in the field of metal ion sensing materials.
- spiropyran is modified to selectively bind metal ions to the derivative anthracene ring; the specific spiropyran derivative can be modified on the surface of the matrix material to selectively bind to specific light under different illumination conditions.
- a functional material for metal ions is modified to selectively bind metal ions to the derivative anthracene ring.
- Macroporous silica is often used as an adsorbent material in the field of environmental water treatment.
- a large number of reports have reported that the macroporous silica modified by grafting has a good adsorption effect on heavy metals in water.
- the object of the present invention is to provide a method for preparing an intelligent photocatalytic degradation-adsorbing material, and the material obtained thereby completely removes hexavalent chromium in water under visible light/ultraviolet light irradiation, which is beneficial to the development of water treatment technology.
- a method for preparing a photocatalytic degradation-adsorption material comprising the steps of:
- the spiropyran derivative is SPNH, and its structure is as follows:
- the template polymer polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P 123) and a certain concentration of sodium sulfate solution are dissolved in the NaAc-Hac solution and stirred uniformly. Then, methyl orthosilicate is added and stirring is continued to obtain a mixture; then the mixture is allowed to stand, and then hydrothermally reacted to obtain a solid, and the obtained solid is calcined at a high temperature to remove the template polymer, and the obtained white solid is a macroporous porous nanometer. Silica foam.
- the concentration of the sodium sulfate solution used above is any one of 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, and 0.4 mol/L, preferably 0.4 mol/L.
- the pH of the NaAc-Hac solution is 4-6, preferably 5.
- the mass ratio of the nano silica foam, citric acid, tin tetrachloride pentachloride and thioacetamide is 1:2.1:3.5:1.5.
- the temperature of the hydrothermal reaction is 130 ° C, 150 ° C or 170 ° C, and further preferably 150 ° C.
- the hydrothermal reaction is between 6 hours, 12 hours, 18 hours or 24 hours, more preferably 12 hours.
- Polypropylene oxide-polyethylene oxide triblock copolymer (P123) is dissolved in NaAc-Hac solution with a certain concentration of sodium sulfate solution and stirred uniformly, then adding methyl orthosilicate and stirring to obtain a mixture; then standing The mixture is hydrothermally reacted to obtain a solid, and the obtained solid is calcined at a high temperature to remove the template polymer, and the obtained white solid is a macroporous porous nano silica foam.
- the concentration of the sodium sulfate solution used above is any one of 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, and 0.4 mol/L, preferably 0.4 mol/L.
- the pH of the NaAc-Hac solution is 4-6, preferably 5.
- the mass ratio of the nano silica foam, the citric acid, the tin tetrachloride pentahydrate and the thioacetamide is 1:2.1:3.5:1.5.
- the temperature of the hydrothermal reaction is 130 ° C, 150 ° C or 170 ° C, and further preferably 150 ° C.
- the hydrothermal reaction is 6 hours, 12 hours, 18 hours or 24 hours, more preferably 12 hours. Catalytic degradation - adsorbed materials.
- the obtained material utilizes SnS ⁇ to degrade Cr(VI) into Cr 3+ ; after degradation, ultraviolet light irradiation can be used to utilize SPNH.
- the anthracene ring structure complexes Cr 3+ to achieve complete removal of chromium ions. Therefore, the product of the present invention can be used for treating chromium ion-containing contaminants, and the present invention also discloses the use of the above photocatalytic degradation-adsorption material as a chromium ion removing material.
- the present invention has the following advantages over the prior art:
- the present invention firstly modifies an amino group on a nano silica foam loaded with a visible light catalyst, and then reacts with succinic anhydride to bond a carboxyl group, and then utilizes a carboxyl group to selectively bind Cr(III) and contains a phenolic hydroxyl group.
- the spiropyran derivative (SPNH) is reacted under the catalytic dehydration of dicyclohexylcarbodiimide (DCC) to obtain a photocatalytic degradation-adsorbing material excellent in the removal of chromium ions.
- the spiropyran component in the modified photosensitive compound can be entangled under ultraviolet light, so that the material can effectively combine with Cr 3+ And release, so that the material can be reused, overcoming the defects that the existing adsorbent materials are difficult to desorb in the water treatment field, and it is difficult to reuse.
- the invention can efficiently utilize the visible light to catalyze the degradation of Cr(VI) by embedding SnS 2 , which is more energy-saving and environmentally friendly than the conventional adsorbent material; the selected porous material of the base material nano silica foam has a porous macroporous structure. Therefore, it has a large specific surface area and can improve the adsorption effect of the material.
- the preparation method of the present invention is simple, and the prepared photocatalytic degradation-adsorption material has stable structure, can effectively remove chromium ions in the waste water, and greatly expands the application of the sewage treatment agent.
- FIG. 1 is a transmission electron micrograph of a nano-silica foam, a SnS 2- loaded nano-silica foam, and a transmission electron microscope effect diagram of each slice; [0029] FIG.
- FIG. 5 is a graph showing the photocatalytic efficiency of the material for different concentrations of K 2 Cr 2 0 7 solution for 90 minutes and the total chromium removal rate after ultraviolet irradiation;
- the solid was collected, washed with water several times, dried, and dispersed again in 200 mL of hydrazine, hydrazine-dimethylformamide, then 500 mg of dicyclohexylcarbodiimide and 250 mg of SPNH were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. Two days, the solid powder obtained by filtration was the prepared photocatalytic degradation-adsorbing material.
- TEM 1 is a transmission electron microscope (TEM) diagram, from left to right, a transmission electron micrograph of nano-silica foam, a transmission electron micrograph of a slice, a transmission electron micrograph of a nano-silica foam loaded with SnS 2 , and a slice.
- the transmission electron micrograph shows that the SnS 2 nanoparticles are successfully embedded in the nano-silica foam.
- N is a full spectrum and a Nls spectrum (XPS) of the above-mentioned photocatalytic degradation-adsorption material by X-ray photoelectron spectroscopy, and it can be seen that N elements of different chemical environments exist in the obtained material, which is KH550 and SPNH. In the N, it can be characterized that SPNH is successfully grafted onto the silica nanofoam.
- XPS Nls spectrum
- said photocatalytic titanium in Synthesis Example taken 50mg degradation - adsorbent was added to 50mL concentration of 50mg / L of 20 "207 aqueous solution, stirred under irradiation of xenon lamp light source simulated visible 20 minutes separated A solid is obtained to obtain an aqueous solution after catalytic degradation.
- FIG. 3 is a comparative photograph of an aqueous solution of K 2 C r 2 0 7 before and after photocatalytic degradation, and it is apparent from the figure that the color of the aqueous solution changes from deep to colorless, thus qualitatively verifying that the photocatalytic degradation-adsorption of the present invention is excellent.
- the catalytic degradation-adsorption material prepared by the invention has good degradation effect and adsorption efficiency for each concentration of Cr(VI), especially for low concentration K 2 Cr 2 0 7 , with nearly 100 % degradation efficiency and removal rate are much greater than the processing level of existing materials.
- the photocatalytic degradation-adsorption material after treating different concentrations of K 2 Cr 2 0 7 aqueous solution in the fifth embodiment is dried, and then placed in 50 mL of an acetic acid solution having a concentration of 0.1 mol/L, under visible light conditions. The mixture was washed under reflux for 2 hours, and then the total chromium concentration in each acetic acid solution was sequentially measured, and the results are shown in Fig. 6.
Abstract
Disclosed are a preparation method and the use of a photocatalytic degradation-adsorption material. The method comprises modifying a visible-light catalyst loaded nano-silicon dioxide foam with amino groups, then reacting with succinic anhydride to connect carboxyl groups, subsequently reacting the carboxyl groups with a spiropyran derivative (SPNH) which can be selectively combined with Cr(III) and contains phenolic hydroxyl groups, under the catalytic dehydration of dicyclohexyl carbodiimide (DCC), so as to obtain photocatalytic degradation-adsorption material which has excellent chromium ion-removing performance. The material thus obtained completely removes hexavalent chromium ions from water under the irradiation of visible light/ultraviolet light, facilitating the development of the water treatment technology.
Description
说明书 发明名称：光催化降解-吸附材料的制备方法与应用 技术领域 Description: The method and application of photocatalytic degradation-adsorption material
[0001] 本发明属于高分子纳米复合材料技术领域， 具体涉及一种智能的光催化降解- 吸附材料的制备方法及在铬离子吸附降解上的应用。 [0001] The invention belongs to the technical field of polymer nano composite materials, and particularly relates to an intelligent photocatalytic degradation-adsorption material preparation method and application thereof to chromium ion adsorption degradation.
背景技术 Background technique
[0002] 随着近年来工业的迅速发展， 人类赖以生存的水资源遭受了严重污染。 水体污 染物中的重金属因不能被生物降解， 相反却能在食物链的生物放大作用下， 成 千百倍地富集， 最后进入人体， 危害人类健康。 铬 (Cr)是常见的危害最大的重金 属之一， 广泛存在于自然环境中， 水环境中铬主要来源于电镀、 冶炼、 制革、 纺织、 印染、 水泥、 钢铁、 油漆、 制药等多达 80种工业废水排放。 水中的铬通 常以六价和三价形式价态存在， 微量的三价铬是人体必需的， 然而过量吋对人 体却有较大的危害， 而且微量的三价铬对水体生物也有较大毒性。 六价铬则为 吞入性毒物 /吸入性极毒物， 皮肤接触可能导致敏感； 更可能造成遗传性基因缺 陷， 吸入可能致癌， 对环境有持久危险性。 因此处理水中 Cr(VI)迫在眉睫， 利用 半导体光催化还原法处理 Cr(VI)是一种有发展前途的废水处理方法。 [0002] With the rapid development of industry in recent years, the water resources that human beings depend on have been seriously polluted. Heavy metals in water pollutants cannot be biodegraded. On the contrary, they can be enriched thousands of times under the biomagnification of the food chain, and finally enter the human body, endangering human health. Chromium (Cr) is one of the most common heavy metals. It is widely found in natural environments. Chromium in water environment mainly comes from electroplating, smelting, tanning, textile, printing and dyeing, cement, steel, paint, pharmaceutical, etc. up to 80 Industrial wastewater discharge. Chromium in water usually exists in the form of hexavalent and trivalent forms. A small amount of trivalent chromium is essential for the human body. However, excessive strontium is harmful to the human body, and trace amounts of trivalent chromium are also highly toxic to aquatic organisms. . Hexavalent chromium is a toxic poison/inhalation of extremely toxic substances. Skin contact may cause sensitivity; it is more likely to cause hereditary genetic defects, and inhalation may cause cancer and endanger the environment. Therefore, the treatment of Cr(VI) in water is imminent. The treatment of Cr(VI) by semiconductor photocatalytic reduction is a promising wastewater treatment method.
[0003] 螺吡喃 （spiropymn) 及其衍生物是目前研究较广泛的一类可作为光幵关的化 合物， 由于其可在紫外 /可见光照射下实现幵环 /闭环的转变， 而幵环下的光致异 构体可与金属离子结合， 因而螺吡喃及其衍生物在金属离子传感材料领域受到 了许多研究者的关注。 已有文献报道将螺吡喃进行改性， 使其衍生物幵环体能 够选择性结合金属离子； 将特定的螺吡喃衍生物修饰在基体材料表面可获得在 不同光照下能够选择性结合特定金属离子的功能材料。 [0003] Spiropymn and its derivatives are currently widely studied as a kind of compound, which can realize the ring/closed loop transition under ultraviolet/visible illumination. The photoisomers can bind to metal ions, and thus spiropyrans and their derivatives have attracted the attention of many researchers in the field of metal ion sensing materials. It has been reported in the literature that spiropyran is modified to selectively bind metal ions to the derivative anthracene ring; the specific spiropyran derivative can be modified on the surface of the matrix material to selectively bind to specific light under different illumination conditions. A functional material for metal ions.
[0004] 大孔多孔二氧化硅常作为吸附材料应用于环境水处理领域， 有大量文献报道接 枝修饰后的大孔多孔二氧化硅对水体中重金属有较好的吸附效果。 [0004] Macroporous silica is often used as an adsorbent material in the field of environmental water treatment. A large number of reports have reported that the macroporous silica modified by grafting has a good adsorption effect on heavy metals in water.
[0005] 至今未见将多孔二氧化硅与螺吡喃化合物复合应用于铬离子光催化吸附降解的 报道； 同吋在水体环境因素一定的情况下， 复合体系内部的稳定性、 协同性以 及表面特性对其处理活性有着重要的影响； 同吋对于铬水处理剂而言， 还需要
具有脱吸附的功能。 [0005] So far, there has been no report on the application of porous silica and spiropyran compounds in the photocatalytic degradation of chromium ions; the stability, synergy and surface of the composite system in the case of certain environmental factors in the water environment. Characteristics have an important influence on its processing activity; for chrome water treatment agents, Has the function of desorption.
技术问题 technical problem
问题的解决方案 Problem solution
技术解决方案 Technical solution
[0006] 本发明目的是提供一种智能光催化降解-吸附材料的制备方法， 由此得到的材 料在可见光 /紫外光照射下完全去除水中六价铬， 有利于水处理技术的发展。 [0006] The object of the present invention is to provide a method for preparing an intelligent photocatalytic degradation-adsorbing material, and the material obtained thereby completely removes hexavalent chromium in water under visible light/ultraviolet light irradiation, which is beneficial to the development of water treatment technology.
[0007] 为达到上述发明目的， 本发明采用的具体技术方案是： [0007] In order to achieve the above object, the specific technical solution adopted by the present invention is:
[0008] 一种光催化降解-吸附材料的制备方法， 包括以下步骤： [0008] A method for preparing a photocatalytic degradation-adsorption material, comprising the steps of:
[0009] (1) 将纳米二氧化硅泡沫分散于去离子水中， 然后加入柠檬酸、 五水四氯化 锡和硫代乙酰胺； 然后于 130〜170°C下水热反应 6〜24小吋， 反应结束后收集反 应混合物中的固体， 得到负载 SnS 2的二氧化硅材料； [0009] (1) dispersing the nano silica foam in deionized water, then adding citric acid, tin tetrachloride and thioacetamide; then hydrothermal reaction at 130~170 ° C for 6 to 24 hours After the reaction is completed, the solid in the reaction mixture is collected to obtain a silica material supporting SnS 2 ;
[0010] (2) 负载 SnS 2的二氧化硅材料经 3-氨基丙基三乙氧基硅烷处理后分散在 Ν,Ν- 二甲基甲酰胺中， 然后加入丁二酸酐进行反应， 反应结束后收集固体； 然后将 收集的固体分散于 Ν,Ν-二甲基甲酰胺中， 再加入二环己基碳二亚胺 （DCC) 和 螺吡喃衍生物 （SPNH) ， 于惰性气氛下反应 12〜48小吋， 过滤反应液得到固体 ， 即为光催化降解 -吸附材料； 所述 SPNH与 DCC的摩尔比为 1: (0.5〜1.5) 。 [0010] (2) The SnS 2- loaded silica material is treated with 3-aminopropyltriethoxysilane, dispersed in hydrazine, hydrazine-dimethylformamide, and then succinic anhydride is added to carry out the reaction, and the reaction is completed. The solid is then collected; the collected solid is then dispersed in hydrazine, hydrazine-dimethylformamide, and then dicyclohexylcarbodiimide (DCC) and spiropyran derivative (SPNH) are added and reacted under an inert atmosphere. ~48 hours, the reaction solution is filtered to obtain a solid, which is a photocatalytic degradation-adsorption material; the molar ratio of SPNH to DCC is 1: (0.5~1.5).
[0011] 本发明中， 螺吡喃衍生物为 SPNH， 其结构如下： [0011] In the present invention, the spiropyran derivative is SPNH, and its structure is as follows:
[0013] 上述所用硫酸钠溶液浓度为 0.1mol/L、 0.2mol/L、 0.3mol/L、 0.4mol/L中的任意 一种， 优选 0.4mol/L。 The concentration of the sodium sulfate solution used above is any one of 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, and 0.4 mol/L, preferably 0.4 mol/L.
[0014] NaAc-Hac溶液的 pH为 4-6， 优选为 5。 The pH of the NaAc-Hac solution is 4-6, preferably 5.
[0015] 上述技术方案中， 步骤 （1) 中， 纳米二氧化硅泡沫、 柠檬酸、 五水四氯化锡 和硫代乙酰胺的质量比为 1:2.1:3.5:1.5。 [0015] In the above technical solution, in the step (1), the mass ratio of the nano silica foam, citric acid, tin tetrachloride pentachloride and thioacetamide is 1:2.1:3.5:1.5.
[0016] 优选的， 步骤 （1) 中， 水热反应的温度为 130°C、 150°C或者 170°C， 进一步优 选为 150°C。 [0016] Preferably, in the step (1), the temperature of the hydrothermal reaction is 130 ° C, 150 ° C or 170 ° C, and further preferably 150 ° C.
[0017] 优选的， 步骤 （1) 中， 水热反应的吋间为 6小吋、 12小吋、 18小吋或者 24小吋 ， 进一步优选为 12小吋。 聚环氧丙烷 -聚环氧乙烷三嵌段共聚物 （P123) 与一定 浓度的硫酸钠溶液溶解在 NaAc-Hac溶液中搅拌均匀， 然后加入正硅酸甲酯继续 搅拌得到混合物； 然后静置混合物， 再进行水热反应得到固体， 将得到的固体 经高温煅烧以去除模板聚合物， 所得白色固体即为大孔多孔纳米二氧化硅泡沫 [0017] Preferably, in the step (1), the hydrothermal reaction is between 6 hours, 12 hours, 18 hours or 24 hours, more preferably 12 hours. Polypropylene oxide-polyethylene oxide triblock copolymer (P123) is dissolved in NaAc-Hac solution with a certain concentration of sodium sulfate solution and stirred uniformly, then adding methyl orthosilicate and stirring to obtain a mixture; then standing The mixture is hydrothermally reacted to obtain a solid, and the obtained solid is calcined at a high temperature to remove the template polymer, and the obtained white solid is a macroporous porous nano silica foam.
[0018] 上述所用硫酸钠溶液浓度为 0.1mol/L、 0.2mol/L、 0.3mol/L、 0.4mol/L中的任意 一种， 优选 0.4mol/L。 The concentration of the sodium sulfate solution used above is any one of 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, and 0.4 mol/L, preferably 0.4 mol/L.
[0019] NaAc-Hac溶液的 pH为 4-6， 优选为 5。 The pH of the NaAc-Hac solution is 4-6, preferably 5.
[0020] 上述技术方案中， 步骤 （1) 中， 纳米二氧化硅泡沫、 柠檬酸、 五水四氯化锡 和硫代乙酰胺的质量比为 1:2.1:3.5:1.5。 [0020] In the above technical solution, in the step (1), the mass ratio of the nano silica foam, the citric acid, the tin tetrachloride pentahydrate and the thioacetamide is 1:2.1:3.5:1.5.
[0021] 优选的， 步骤 （1) 中， 水热反应的温度为 130°C、 150°C或者 170°C， 进一步优 选为 150°C。 [0021] Preferably, in the step (1), the temperature of the hydrothermal reaction is 130 ° C, 150 ° C or 170 ° C, and further preferably 150 ° C.
[0022] 优选的， 步骤 （1) 中， 水热反应的吋间为 6小吋、 12小吋、 18小吋或者 24小吋 ， 进一步优选为 12小吋。 催化降解 -吸附材料。 [0022] Preferably, in the step (1), the hydrothermal reaction is 6 hours, 12 hours, 18 hours or 24 hours, more preferably 12 hours. Catalytic degradation - adsorbed materials.
[0023] 本发明公幵的光催化降解 -吸附材料， 在可见光下， 所获得的材料利用 SnS ^ 化降解 Cr(VI)成为 Cr 3+; 降解完毕后， 利用紫外光照射， 可利用 SPNH的幵环结 构络合 Cr 3+， 从而实现铬离子的完全去除。 因此本发明的产品可以用于处理含铬 离子的污染物， 所以本发明还公幵了上述光催化降解 -吸附材料作为铬离子去除 材料的应用。
发明的有益效果 [0023] In the photocatalytic degradation-adsorption material of the present invention, under visible light, the obtained material utilizes SnS^ to degrade Cr(VI) into Cr 3+ ; after degradation, ultraviolet light irradiation can be used to utilize SPNH. The anthracene ring structure complexes Cr 3+ to achieve complete removal of chromium ions. Therefore, the product of the present invention can be used for treating chromium ion-containing contaminants, and the present invention also discloses the use of the above photocatalytic degradation-adsorption material as a chromium ion removing material. Advantageous effects of the invention
有益效果 Beneficial effect
[0024] 由于上述技术方案运用， 本发明与现有技术相比具有下列优点： [0024] Due to the above technical solutions, the present invention has the following advantages over the prior art:
[0025] 1.本发明首次在负载了可见光催化剂的纳米二氧化硅泡沫上修饰氨基， 然后与 丁二酸酐反应以连接羧基， 再利用羧基与可选择性结合 Cr(III)且含有酚羟基的螺 吡喃衍生物 （SPNH) 在二环己基碳二亚胺 （DCC) 催化脱水下进行反应， 得到 去除铬离子性能优异的光催化降解 -吸附材料。 [0025] 1. The present invention firstly modifies an amino group on a nano silica foam loaded with a visible light catalyst, and then reacts with succinic anhydride to bond a carboxyl group, and then utilizes a carboxyl group to selectively bind Cr(III) and contains a phenolic hydroxyl group. The spiropyran derivative (SPNH) is reacted under the catalytic dehydration of dicyclohexylcarbodiimide (DCC) to obtain a photocatalytic degradation-adsorbing material excellent in the removal of chromium ions.
[0026] 2.本发明得到的微光催化降解-吸附材料中， 所修饰的光敏化合物中的螺吡喃 组分可以在紫外光照射下幵环， 从而使材料对 Cr 3+能有效地结合与释放， 使得材 料可以重复使用， 克服了现有吸附材料在水处理领域脱吸附困难， 难以重复利 用的缺陷。 2. In the microphotocatalytic degradation-adsorption material obtained by the invention, the spiropyran component in the modified photosensitive compound can be entangled under ultraviolet light, so that the material can effectively combine with Cr 3+ And release, so that the material can be reused, overcoming the defects that the existing adsorbent materials are difficult to desorb in the water treatment field, and it is difficult to reuse.
[0027] 3.本发明通过嵌入 SnS 2可高效的利用可见光对 Cr(VI)进行催化降解， 相比传统 吸附材料更节能环保； 所选的基底材料纳米二氧化硅泡沫具有的多孔大孔结构 ， 从而具有较大的比表面积， 能够提高材料的吸附效果。 [0027] 3. The invention can efficiently utilize the visible light to catalyze the degradation of Cr(VI) by embedding SnS 2 , which is more energy-saving and environmentally friendly than the conventional adsorbent material; the selected porous material of the base material nano silica foam has a porous macroporous structure. Therefore, it has a large specific surface area and can improve the adsorption effect of the material.
[0028] 4.本发明公幵的制备方法简单， 制备的光催化降解-吸附材料结构稳定， 能够 有效地去除掉废水中的铬离子， 大大拓展了污水处理剂的应用。 [0028] 4. The preparation method of the present invention is simple, and the prepared photocatalytic degradation-adsorption material has stable structure, can effectively remove chromium ions in the waste water, and greatly expands the application of the sewage treatment agent.
对附图的简要说明 Brief description of the drawing
附图说明 DRAWINGS
[0029] 图 1为纳米二氧化硅泡沫、 SnS 2附载的纳米二氧化硅泡沫的透射电镜图与各自 切片的透射电镜效果图； 1 is a transmission electron micrograph of a nano-silica foam, a SnS 2- loaded nano-silica foam, and a transmission electron microscope effect diagram of each slice; [0029] FIG.
[0030] 图 2为光催化降解 -吸附材料的 X射线光电子能谱分析全谱与 Nls谱图； 2 is a full spectrum and Nls spectrum of X-ray photoelectron spectroscopy analysis of photocatalytic degradation-adsorbing materials;
[0031] 图 3为 50mg/L的 K 2Cr 20 7光照催化降解前后对比图； 3 is a comparison chart before and after photocatalytic degradation of 50 mg/L K 2 Cr 2 0 7 ;
[0032] 图 4为材料光催化降解、 吸附后的 Cr元素 X射线光电子能谱分析谱图； 4 is a photoelectron spectroscopy spectrum of a Cr element after photocatalytic degradation and adsorption of a material;
[0033] 图 5为材料对不同浓度 K 2Cr 20 7溶液的 90分钟的光催化效率及其后紫外照射的 总铬去除率图； [0033] FIG. 5 is a graph showing the photocatalytic efficiency of the material for different concentrations of K 2 Cr 2 0 7 solution for 90 minutes and the total chromium removal rate after ultraviolet irradiation;
[0034] 图 6为材料对不同浓度 K 2Cr 20 7溶液催化 -吸附后的解吸附效率图。
本发明的实施方式 6 is a graph showing the desorption efficiency of a material after catalytic-adsorption of different concentrations of K 2 Cr 2 0 7 solution. Embodiments of the invention
[0035] 下面结合附图及实施例对本发明作进一步描述： [0035] The present invention will be further described below in conjunction with the accompanying drawings and embodiments:
[0036] 实施例一 [0036] Embodiment 1
[0037] 在 30。C下， 将 l.OOg聚环氧乙烷 -聚环氧丙烷 -聚环氧乙烷三嵌段共聚物 （P123) 与 0.85g Na 2SO 4 (0.20mol/L) 溶液溶解在 25.00g pH=6的 NaAC-HAc缓冲溶液中[0037] At 30. C. Dissolve 1.000g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) with 0.85g of Na 2 SO 4 (0.20mol/L) solution at 25.00g pH =6 in NaAC-HAc buffer solution
， 搅拌均匀。 然后向该混合液中加入 1.52g正硅酸甲酯， 继续搅拌 10分钟， 随后 静置 20小吋。 再将静置后的混合物于不锈钢反应釜中于 100°C水热反应 24小吋。 将反应后的白色固体收集、 多次用蒸馏水洗涤并室温干燥。 最后将该白色固体 粉末于管式炉中在 550°C下高温煅烧 4小吋。 最终产物为白色蓬松状粉末， 为纳米 二氧化硅泡沫。 , Stir well. Then, 1.52 g of methyl orthosilicate was added to the mixture, and stirring was continued for 10 minutes, followed by allowing to stand for 20 hours. The static mixture was hydrothermally reacted at 100 ° C for 24 hours in a stainless steel autoclave. The white solid after the reaction was collected, washed with distilled water several times, and dried at room temperature. Finally, the white solid powder was calcined at a high temperature of 550 ° C for 4 hours in a tube furnace. The final product was a white fluffy powder which was a nanosilica foam.
[0038] 称取 500mg纳米二氧化硅泡沫分散于 40mL去离子水中， 然后加入 1.052g柠檬酸 、 1.753g五水四氯化锡和 751.3mg硫代乙酰胺， 搅拌溶解后倒入 50mL不锈钢水热 反应釜， 置于 160°C下反应 20小吋。 最后将反应混合物离心分离得到黄色固体， 并依次用乙醇、 蒸馏水洗涤。 得到负载了 SnS 纳米二氧化硅泡沫。 [0038] Weigh 500mg nano silica foam dispersed in 40mL deionized water, then add 1.052g citric acid, 1.753g tin tetrachloride pentahydrate and 751.3mg thioacetamide, stir and dissolve, then pour into 50mL stainless steel water heat The reaction kettle was placed at 160 ° C for 20 hours. Finally, the reaction mixture was centrifuged to obtain a yellow solid, which was washed sequentially with ethanol and distilled water. A SnS nanosilica foam was obtained.
[0039] 将 350mg负载了 SnS 2的纳米二氧化硅泡沫分散在 200mL乙腈中， 室温搅拌下滴 力口 5mL 3-氨基丙基三乙氧基硅烷 （KH550) ， 继续搅拌 12小吋后收集固体并重新 分散在 300mL N,N-二甲基甲酰胺中， 加入 4.5g丁二酸酐， 室温下继续搅拌 20小吋 。 反应结束后收集固体， 多次水洗后晾干， 并再次分散于 200mL的 Ν,Ν-二甲基甲 酰胺中， 然后加入 500mg二环己基碳二亚胺和 250mg SPNH， 氮气气氛下， 室温 搅拌一天， 过滤得到固体粉末即为所制备的光催化降解 -吸附材料。 [0039] 350 mg of SnS 2 loaded nano silica foam was dispersed in 200 mL of acetonitrile, and 5 mL of 3-aminopropyltriethoxysilane (KH550) was added dropwise at room temperature with stirring. After stirring for 12 hours, solids were collected. It was redispersed in 300 mL of N,N-dimethylformamide, 4.5 g of succinic anhydride was added, and stirring was continued for 20 hours at room temperature. After the reaction, the solid was collected, washed with water several times, dried, and dispersed again in 200 mL of hydrazine, hydrazine-dimethylformamide, then 500 mg of dicyclohexylcarbodiimide and 250 mg of SPNH were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. One day, a solid powder obtained by filtration is the prepared photocatalytic degradation-adsorbing material.
[0040] 实施例二 [0040] Embodiment 2
[0041] 在 35。C下， 将 l.OOg聚环氧乙烷 -聚环氧丙烷 -聚环氧乙烷三嵌段共聚物 （P123) 与 1.70g Na 2SO 4 (0.40mol/L) 溶液溶解在 30.00g pH=5的 NaAC-HAc缓冲溶液中[0041] At 35. C. Dissolve 1.000g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and 1.70g of Na 2 SO 4 (0.40mol/L) solution at 30.00g pH. =5 in NaAC-HAc buffer solution
， 搅拌均匀。 然后向该混合液中加入 1.52g正硅酸甲酯， 继续搅拌 5分钟， 随后静 置 24小吋。 再将静置后的混合物于不锈钢反应釜中于 100°C水热反应 24小吋。 将 反应后的白色固体收集、 多次用蒸馏水洗涤并室温干燥。 最后将该白色固体粉 末于管式炉中在 550°C下高温煅烧 5小吋。 最终产物为白色蓬松状粉末， 为纳米二 氧化硅泡沫。
[0042] 称取 500mg纳米二氧化硅泡沫分散于 40mL去离子水中， 然后加入 1.052g柠檬酸 、 1.753g五水四氯化锡和 751.3mg硫代乙酰胺， 搅拌溶解后倒入 50mL不锈钢水热 反应釜， 置于 150°C下反应 12小吋。 最后将反应混合物离心分离得到黄色固体， 并依次用乙醇、 蒸馏水洗涤。 得到负载了 SnS 纳米二氧化硅泡沫。 , Stir well. Then, 1.52 g of methyl orthosilicate was added to the mixture, stirring was continued for 5 minutes, and then allowed to stand for 24 hours. The static mixture was hydrothermally reacted at 100 ° C for 24 hours in a stainless steel autoclave. The white solid after the reaction was collected, washed with distilled water several times, and dried at room temperature. Finally, the white solid powder was calcined at a high temperature of 550 ° C for 5 hours in a tube furnace. The final product was a white fluffy powder and was a nanosilica foam. [0042] Weigh 500mg nano silica foam dispersed in 40mL deionized water, then add 1.052g citric acid, 1.753g tin tetrachloride pentahydrate and 751.3mg thioacetamide, stir and dissolve, then pour into 50mL stainless steel water heat The reaction vessel was reacted at 150 ° C for 12 hours. Finally, the reaction mixture was centrifuged to obtain a yellow solid, which was washed sequentially with ethanol and distilled water. The SnS nanosilica foam was loaded.
[0043] 将 300mg负载了 SnS 2的纳米二氧化硅泡沫分散在 200mL乙腈中， 室温搅拌下滴 力口 5mL 3-氨基丙基三乙氧基硅烷 （KH550) ， 继续搅拌 12小吋后收集固体并重新 分散在 300mL N,N-二甲基甲酰胺中， 加入 5g丁二酸酐， 室温下继续搅拌 24小吋 。 反应结束后收集固体， 多次水洗后晾干， 并再次分散于 200mL的 Ν,Ν-二甲基甲 酰胺中， 然后加入 500mg二环己基碳二亚胺和 250mg SPNH， 氮气气氛下， 室温 搅拌两天， 过滤得到固体粉末即为所制备的光催化降解 -吸附材料。 [0043] 300 mg of SnS 2 loaded nano silica foam was dispersed in 200 mL of acetonitrile, and 5 mL of 3-aminopropyltriethoxysilane (KH550) was added dropwise at room temperature, and stirring was continued for 12 hours. It was redispersed in 300 mL of N,N-dimethylformamide, and 5 g of succinic anhydride was added thereto, and stirring was continued for 24 hours at room temperature. After the reaction, the solid was collected, washed with water several times, dried, and dispersed again in 200 mL of hydrazine, hydrazine-dimethylformamide, then 500 mg of dicyclohexylcarbodiimide and 250 mg of SPNH were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. Two days, the solid powder obtained by filtration was the prepared photocatalytic degradation-adsorbing material.
[0044] 图 1为透射电镜 （TEM) 图， 从左至右依次为纳米二氧化硅泡沫的透射电镜图 、 切片的透射电镜图、 负载 SnS 2的纳米二氧化硅泡沫的透射电镜图、 切片的透 射电镜图， 可明显看出， 在纳米二氧化硅泡沫中成功嵌入了 SnS 2纳米粒子。 1 is a transmission electron microscope (TEM) diagram, from left to right, a transmission electron micrograph of nano-silica foam, a transmission electron micrograph of a slice, a transmission electron micrograph of a nano-silica foam loaded with SnS 2 , and a slice. The transmission electron micrograph shows that the SnS 2 nanoparticles are successfully embedded in the nano-silica foam.
[0045] 图 2为上述光催化降解 -吸附材料的 X射线光电子能谱分析全谱与 Nls谱图 （XPS ) ， 可以看出所得的材料中存在不同化学环境的 N元素， 正是 KH550与 SPNH中 的 N， 因此可以表征 SPNH成功接枝于二氧化硅纳米泡沫上。 2 is a full spectrum and a Nls spectrum (XPS) of the above-mentioned photocatalytic degradation-adsorption material by X-ray photoelectron spectroscopy, and it can be seen that N elements of different chemical environments exist in the obtained material, which is KH550 and SPNH. In the N, it can be characterized that SPNH is successfully grafted onto the silica nanofoam.
[0046] 实施例三 [0046] Embodiment 3
[0047] 称取 50mg实施例二中合成的光催化降解 -吸附材料， 加入到 50mL浓度为 50mg/L 的 20" 207水溶液中， 在氙灯光源模拟的可见光照射下搅拌 20分钟。 分离出固 体， 得到催化降解后的水溶液。 [0047] said photocatalytic titanium in Synthesis Example taken 50mg degradation - adsorbent was added to 50mL concentration of 50mg / L of 20 "207 aqueous solution, stirred under irradiation of xenon lamp light source simulated visible 20 minutes separated A solid is obtained to obtain an aqueous solution after catalytic degradation.
[0048] 图 3是光照催化降解前后的K 2Cr 20 7水溶液对比照片， 由图明显看出水溶液的 颜色由深变为无色， 因此定性验证本发明的光催化降解-吸附具有优异的铬离子 催化降解效果。 3 is a comparative photograph of an aqueous solution of K 2 C r 2 0 7 before and after photocatalytic degradation, and it is apparent from the figure that the color of the aqueous solution changes from deep to colorless, thus qualitatively verifying that the photocatalytic degradation-adsorption of the present invention is excellent. The catalytic effect of chromium ion catalysis.
[0049] 实施例四 [0049] Embodiment 4
[0050] 称取 50mg实施例二中合成的光催化降解 -吸附材料， 加入到 50mL浓度为 20mg/L 的 K 2Cr 207水溶液中， 在氙灯光源模拟的可见光照射下搅拌 60分钟后改用紫外 光照射半小吋。 然后分离出固体催化降解 -吸附材料， 室温晾干后用于 XPS测试 分析， 得到催化降解-吸附材料中的 Cr元素 XPS谱图， 如图 4所示； 图中所显示的
Cr元素均是 C 环境下的 Cr元素而无 Cr(VI)， 因此可以说明 Cr(VI)完全被催化降 解并被吸附在材料上。 [0050] Weigh 50mg of the photocatalytic degradation-adsorbing material synthesized in the second embodiment, and add it to 50mL of a 20mg/L K 2 Cr 2 0 7 aqueous solution, and stir it under visible light irradiation simulated by a xenon lamp source for 60 minutes. Irradiation with ultraviolet light for half a small flaw. Then, the solid catalytic degradation-adsorption material is separated and dried at room temperature for XPS test analysis to obtain the XP element spectrum of the Cr element in the catalytic degradation-adsorption material, as shown in Fig. 4; Cr element is Cr element in C environment without Cr(VI), so it can be said that Cr(VI) is completely degraded by catalysis and adsorbed on the material.
[0051] 实施例五 [0051] Embodiment 5
[0052] 分别取 50mg实施例二中合成的光催化降解 -吸附材料， 依次加入到 10、 20、 30 、 40、 50、 70、 100mg/L的 K 2Cr 207水溶液中， 各用可见光照射 90分钟， 然后于 紫外光照射下一小吋， 过滤去除固体。 分别取可见光照射和紫外光光照后的水 样， 并利用紫外分光光度法测试可见光催化后的 Cr(VI)浓度， 利用原子吸收光谱 法测试紫外光照射后的总 Cr浓度， 分别计算材料对不同浓度 K 2Cr 20 7溶液的催 化降解效率与总 Cr去除率， 得到结果如图 5所示。 [0052] Take 50mg of the photocatalytic degradation-adsorption material synthesized in the second embodiment, and sequentially add to 10, 20, 30, 40, 50, 70, 100 mg / L of K 2 Cr 2 0 7 aqueous solution, each using visible light After irradiation for 90 minutes, the cells were irradiated with ultraviolet light for a while, and the solid was removed by filtration. The water samples after visible light irradiation and ultraviolet light irradiation were respectively taken, and the Cr(VI) concentration after visible light catalysis was measured by ultraviolet spectrophotometry. The total Cr concentration after ultraviolet light irradiation was measured by atomic absorption spectrometry, and the material pairs were calculated separately. The catalytic degradation efficiency and the total Cr removal rate of the K 2 Cr 2 0 7 solution were obtained as shown in FIG. 5 .
[0053] 由图 5可见， 本发明制备的催化降解-吸附材料对各个浓度的 Cr(VI)均有较好的 降解效果和吸附效率， 尤其对低浓度 K 2Cr 207， 拥有近 100%的降解效率和去除 率， 远大于现有材料的处理水平。 [0053] It can be seen from FIG. 5 that the catalytic degradation-adsorption material prepared by the invention has good degradation effect and adsorption efficiency for each concentration of Cr(VI), especially for low concentration K 2 Cr 2 0 7 , with nearly 100 % degradation efficiency and removal rate are much greater than the processing level of existing materials.
[0054] 实施例六 [0054] Embodiment 6
[0055] 将实施案例五中处理不同浓度 K 2Cr 20 7水溶液后的光催化降解-吸附材料烘干 ， 然后分别置于 50mL浓度为 O.Olmol/L的醋酸溶液中， 在可见光条件下回流洗涤 2小吋， 随后依次测量各个醋酸溶液中的总铬浓度， 得到结果如图 6所示。 [0055] The photocatalytic degradation-adsorption material after treating different concentrations of K 2 Cr 2 0 7 aqueous solution in the fifth embodiment is dried, and then placed in 50 mL of an acetic acid solution having a concentration of 0.1 mol/L, under visible light conditions. The mixture was washed under reflux for 2 hours, and then the total chromium concentration in each acetic acid solution was sequentially measured, and the results are shown in Fig. 6.
[0056] 由图 6可知， 可用稀酸解吸附处理六价铬后的降解-吸附材料具有较好的效果， 说明本发明的光催化降解-吸附材料具有脱吸附的功能， 可重复利用。
6 shows that the degradation-adsorbing material after the hexavalent chromium can be desorbed by dilute acid has a good effect, indicating that the photocatalytic degradation-adsorbing material of the present invention has a desorption function and can be reused.
Claims
[权利要求 1] 一种光催化降解-吸附材料的制备方法， 其特征在于， 包括以下步骤 [Claim 1] A method for preparing a photocatalytic degradation-adsorbing material, comprising the following steps
(1) 将纳米二氧化硅泡沫分散于去离子水中， 然后加入柠檬酸、 五 水四氯化锡和硫代乙酰胺； 然后于 130〜170°C下水热反应 6〜24小吋(1) Dispersing the nano silica foam in deionized water, then adding citric acid, tin tetrachloride and thioacetamide; then hydrothermal reaction at 130~170 ° C 6~24 hours
， 反应结束后收集反应混合物中的固体， 得到负载 SnS 2的二氧化石 j 材料； After the reaction is completed, the solid in the reaction mixture is collected to obtain a SnS 2 -loaded silica stone j material;
(2) 负载 SnS 2的二氧化硅材料经 3-氨基丙基三乙氧基硅烷处理后分 散在 Ν,Ν-二甲基甲酰胺中， 然后加入丁二酸酐进行反应， 反应结束后 收集固体； 然后将收集的固体分散于 Ν,Ν-二甲基甲酰胺中， 再加入二 环己基碳二亚胺和螺吡喃衍生物， 于惰性气氛下反应 12〜48小吋， 过 滤反应液得到固体， 即为光催化降解 -吸附材料； 所述螺吡喃衍生物 与二环己基碳二亚胺的摩尔比为 1: (0.5〜1.5) 。 (2) The silica material loaded with SnS 2 is treated with 3-aminopropyltriethoxysilane, dispersed in hydrazine, hydrazine-dimethylformamide, and then succinic anhydride is added to carry out the reaction. After the reaction, solids are collected. Then, the collected solid is dispersed in hydrazine, hydrazine-dimethylformamide, and then dicyclohexylcarbodiimide and spiropyran derivative are added, and the reaction mixture is reacted under an inert atmosphere for 12 to 48 hours, and the reaction liquid is filtered. The solid, that is, the photocatalytic degradation-adsorbing material; the molar ratio of the spiropyran derivative to the dicyclohexylcarbodiimide is 1: (0.5 to 1.5).
[权利要求 2] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于： 纳米二氧化硅泡沫的制备为， 将聚环氧乙烷 -聚环氧丙烷 -聚环氧乙烷 三嵌段共聚物与硫酸钠溶液溶解在 NaAc-Hac溶液中， 搅拌均匀， 然 后加入正硅酸甲酯继续搅拌得到混合物； 然后静置混合物， 再进行水 热反应得到固体， 将得到的固体高温煅烧， 所得白色固体即为纳米二 氧化硅泡沫。 [Claim 2] The method for preparing a photocatalytic degradation-adsorbing material according to claim 1, wherein: the nano silica foam is prepared by using polyethylene oxide-polypropylene oxide-polyethylene oxide The alkane triblock copolymer and the sodium sulfate solution are dissolved in the NaAc-Hac solution, stirred uniformly, and then the methyl orthosilicate is added and stirring is continued to obtain a mixture; then the mixture is allowed to stand, and then hydrothermally reacted to obtain a solid, and the obtained solid is obtained. Calcination at high temperature, the resulting white solid is a nanosilica foam.
[权利要求 3] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于： 步骤 （1) 中， 纳米二氧化硅泡沫、 柠檬酸、 五水四氯化锡和硫代乙 酰胺的质量比为 1:2.1:3.5:1.5。 [Claim 3] The method for preparing a photocatalytic degradation-adsorbing material according to claim 1, wherein: in the step (1), the nano silica foam, citric acid, tin tetrachloride pentachloride, and thioethane B The mass ratio of the amide was 1:2.1:3.5:1.5.
[权利要求 4] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于： 步骤 （1) 中， 水热反应的温度为 130°C、 150°C或者 170°C; 水热反应 的吋间为 6小吋、 12小吋、 18小吋或者 24小吋。 [Claim 4] The method for preparing a photocatalytic degradation-adsorbing material according to claim 1, wherein: in the step (1), the temperature of the hydrothermal reaction is 130 ° C, 150 ° C or 170 ° C; The heat-reacted daytime is 6 hours, 12 hours, 18 hours or 24 hours.
[权利要求 5] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于： 步骤 （1) 中， 所述纳米二氧化硅泡沫的平均孔径为 100nm。 [Claim 5] The method for producing a photocatalytic degradation-adsorbing material according to claim 1, wherein in the step (1), the nano silica foam has an average pore diameter of 100 nm.
[权利要求 6] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于：
步骤 （2) 中， 所述螺吡喃衍生物与二环己基碳二亚胺的摩尔比为 1:1 [Claim 6] The method for preparing a photocatalytic degradation-adsorbing material according to claim 1, wherein: In the step (2), the molar ratio of the spiropyran derivative to the dicyclohexylcarbodiimide is 1:1.
[权利要求 7] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于： 步骤 （2) 中， 负载 SnS 2 [Claim 7] The method for preparing a photocatalytic degradation-adsorbing material according to claim 1, wherein: in the step (2), the load is SnS 2
的二氧化硅材料分散在乙腈中， 搅拌下滴加 3-氨基丙基三乙氧基硅烷 ， 继续搅拌 12小吋， 收集固体即得到经 3-氨基丙基三乙氧基硅烷处理 的负载 SnS 2的二氧化硅材料。 The silica material was dispersed in acetonitrile, 3-aminopropyltriethoxysilane was added dropwise with stirring, stirring was continued for 12 hours, and the solid was collected to obtain a supported SnS treated with 3-aminopropyltriethoxysilane. 2 silica material.
[权利要求 8] 根据权利要求 1所述光催化降解-吸附材料的制备方法， 其特征在于： 步骤 （1) 中， 反应结束后收集反应混合物中的固体， 固体经醇洗、 水洗， 得到负载 SnS 2的二氧化硅材料； 步骤 （2) 中， 反应结束后收 集的固体经水洗、 晾干后再分散于 Ν,Ν-二甲基甲酰胺中； 过滤反应液 得到的固体经醇洗后得到光催化降解 -吸附材料。 [Claim 8] The method for preparing a photocatalytic degradation-adsorbing material according to claim 1, wherein in the step (1), the solid in the reaction mixture is collected after the reaction is completed, and the solid is washed with alcohol and washed with water to obtain a load. The silica material of SnS 2 ; in step (2), the solid collected after the reaction is washed with water, dried, and then dispersed in hydrazine, hydrazine-dimethylformamide; the solid obtained by filtering the reaction solution is washed with alcohol A photocatalytic degradation-adsorption material is obtained.
[权利要求 9] 根据权利要求 1〜8所述任意一种光催化降解-吸附材料的制备方法制 备的光催化降解 -吸附材料。 [Claim 9] A photocatalytic degradation-adsorption material prepared by the method for producing a photocatalytic degradation-adsorption material according to any one of claims 1 to 8.
[权利要求 10] 权利要求 9所述光催化降解 -吸附材料作为铬离子去除材料的应用。
[Claim 10] The photocatalytic degradation-adsorption material according to claim 9 is used as a chromium ion removing material.
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| CN110090491A (en) * | 2019-05-28 | 2019-08-06 | 上海蓝宇水处理股份有限公司 | A kind of filter medium for water process purification |
| US20200158948A1 (en) * | 2018-11-21 | 2020-05-21 | Paul K. Westerhoff | Photoresponsive polymer coated optical fibers for water treatment |
| US11760663B2 (en) | 2016-04-27 | 2023-09-19 | Arizona Board Of Regents On Behalf Of Arizona State University | Fiber-optic integrated membrane reactor |
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