CN116786087B - Preparation method and application of PAMAM (polyamide-amine) and sulfhydryl-containing composite aerogel - Google Patents
Preparation method and application of PAMAM (polyamide-amine) and sulfhydryl-containing composite aerogel Download PDFInfo
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- CN116786087B CN116786087B CN202311062392.XA CN202311062392A CN116786087B CN 116786087 B CN116786087 B CN 116786087B CN 202311062392 A CN202311062392 A CN 202311062392A CN 116786087 B CN116786087 B CN 116786087B
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- 239000004964 aerogel Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 229920000962 poly(amidoamine) Polymers 0.000 title claims abstract description 59
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 166
- 238000001179 sorption measurement Methods 0.000 claims abstract description 154
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 82
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 68
- 239000000661 sodium alginate Substances 0.000 claims abstract description 68
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 56
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000975 dye Substances 0.000 claims abstract description 16
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims abstract description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 135
- 239000000243 solution Substances 0.000 claims description 49
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 21
- 230000002829 reductive effect Effects 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 6
- 239000000182 glucono-delta-lactone Substances 0.000 claims description 6
- 229960003681 gluconolactone Drugs 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229940087646 methanolamine Drugs 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- -1 alkoxy silicon Chemical compound 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000012678 divergent method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 229910002056 binary alloy Inorganic materials 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
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- 239000000499 gel Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229940052223 basic fuchsin Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 2
- 229940107698 malachite green Drugs 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 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
- 239000004952 Polyamide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising 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
- B01J20/02—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
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- 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
- B01J20/28047—Gels
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of PAMAM and mercapto-containing composite aerogel. Synthesizing 1.0 (G1.0) and 2.0 (G2.0) alkoxy silicon-based PAMAM dendrimer by taking 3-aminopropyl triethoxysilane (G0) as a central core and adopting a divergent method; then preparing silica nano particles containing PAMAM dendrimer and mercaptopropyl by sol-gel reaction of G1.0, G2.0 and 3-mercaptopropyl trimethoxy silane (MPTMS), respectively; further compounding the PAMAM dendrimer with GO and SA to prepare the silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimer and mercaptopropyl. The aerogel prepared by the method has more abundant functional groups and more content, can be suitable for adsorption separation of various pollutants such as metal ions, dyes and the like, and has obviously improved adsorption quantity.
Description
Technical Field
The invention relates to the field of aerogel preparation and sewage treatment, in particular to a preparation method and application of PAMAM and mercapto-containing composite aerogel.
Background
The wastewater produced in the electroplating, metallurgy, mining and other industries generally contains Cd (II). Cd (II) is one of the most toxic heavy metal ions, and even in a trace concentration, the Cd (II) can cause serious harm to human health. Therefore, the removal of Cd (II) in the water body by an adsorption method has important significance for protecting the ecological system and human health. The nitrogen-containing functional groups are often used for constructing adsorption separation materials, and Cd (II) in water is efficiently removed. For example, prabu et alAmino-functionalized Fe 3 O 4 @SiO 2 And is used for efficiently adsorbing Cd (II) in the aqueous solution. Marjani et al prepared a carboxylic acid functionalized fibrous silica/polyamide composite and used to adsorb Cd (II) in a body of water. Sun et al prepared chitosan and Fe 3 O 4 The modified fishbone carbon composite material is used for adsorbing Cd (II) in water.
The polyamide-amine dendrimer (PAMAM) is a hyperbranched polymer, has the advantages of high symmetry in structure, cavities in molecules, layering in arrangement of a large number of N, O functional groups, easiness in combination with metal ions, and realization of efficient adsorption and separation of pollutants such as metal ions and dyes. However, PAMAM dendrimers and their complexes are readily soluble in water and are not readily applicable to the field of adsorptive separation. The simple method at present uses alkoxy silicon-based dendrimer and tetraethoxysilane as precursors, prepares silica nanoparticles containing PAMAM dendrimer by sol-gel method, and then applies the silica nanoparticles to the adsorption separation of pollutants in water. However, the ultrafine granularity of the silica nanoparticles makes the silica nanoparticles difficult to recover after adsorption separation, and secondary pollution is easily caused.
The currently reported sodium alginate composite aerogel is mostly suitable for a single pollutant system, for example, wang et al prepare sodium alginate immobilized amino functionalized silica nanoparticles, and apply the sodium alginate immobilized amino functionalized silica nanoparticles to the adsorption separation of U (VI); li and the like are used for preparing sodium alginate/graphene oxide/silicon dioxide composite aerogel for absorbing oil. The existing adsorbent can not meet the requirement of cooperative integrated adsorption separation of various pollutants in complex water bodies.
Therefore, the invention provides the silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and sulfhydryl groups, which can be used for carrying out synergistic integrated adsorption separation on various pollutants in a complex water body, and the technical problem to be solved by the technicians in the field is needed to be solved.
Disclosure of Invention
In view of the above, the invention synthesizes 1.0 and 2.0 generation alkoxy silicon-based PAMAM dendrimers (G1.0 and G2.0) by using 3-aminopropyl triethoxysilane (G0) as a central core and adopting a divergent method; then preparing silica nano particles containing PAMAM dendrimer and mercaptopropyl by sol-gel reaction of G1.0, G2.0 and 3-mercaptopropyl trimethoxy silane respectively; further compounding the PAMAM dendrimer with GO and SA to prepare the silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimer and mercaptopropyl.
The sodium alginate is a natural gel, and the molecules of the sodium alginate can form a crosslinked gel structure through calcium ions, and the sodium alginate is widely applied to carriers for fixing nano particles, bacteria, enzymes and other substances. Sodium alginate contains abundant hydroxyl and carboxyl functional groups, and can promote the adsorption of metal ions and dyes, however, pure sodium alginate aerogel is compact, fragile and poor in mechanical property. Graphene oxide is one of the derivatives of graphene, is a two-dimensional flaky material, has the advantages of large specific surface area, stable chemical property and good mechanical property, contains rich hydroxyl (OH), carboxyl (COOH), epoxy (C-O-C) and other oxygen-containing functional groups, and enables the graphene oxide to have good dispersibility in water or even some organic solvents, so that the graphene oxide has good adsorption performance on heavy metal ions and dyes in water, and based on the adsorption performance, the PAMAM dendrimer-containing silica nanoparticles are fixed in sodium alginate aerogel and then are compounded with the graphene oxide, so that the mechanical strength of sodium alginate can be improved, the functional group types of the sodium alginate aerogel can be enriched, the adaptability of the sodium alginate aerogel to complex water environment can be improved, and the problem that the silica nanoparticles are difficult to recover and reutilize after being adsorbed can be solved.
The invention adopts the following technical scheme to realize the purposes:
a preparation method of PAMAM and mercapto-containing composite aerogel comprises the following steps:
(1) Preparation G1.0: the 3-aminopropyl triethoxysilane is marked as G0, and the amino group is marked as N 2 Under the protection, dissolving methyl acrylate and G0 in methanol, stirring at 25 ℃ for reaction for 24 hours, and distilling under reduced pressure to remove methanol and redundant methyl acrylate after the reaction is completed, so as to obtain a product, namely G0.5; dissolving G0.5Dissolving in methanol at 0deg.C, N 2 Under the protection, dropwise adding a methanol solution of G0.5 into a mixed solution containing ethylenediamine and methanol, keeping the temperature at 0 ℃ and stirring for 0.5h, then heating to 25 ℃ and continuously stirring for reaction for 96h, and removing the methanol and the ethylenediamine through reduced pressure distillation after the reaction is finished to obtain a product, namely G1.0;
(2) Preparation G2.0: methyl acrylate and G1.0 were first dissolved in methanol at N 2 Stirring for 0.5h at 0 ℃ under protection, then heating to 25 ℃ and continuing stirring for reaction for 24h, and removing methanol and redundant methyl acrylate by reduced pressure distillation after the reaction is finished to obtain a product which is marked as G1.5; dissolving G1.5 in methanol at 0deg.C, N 2 Under the protection, dripping the mixture into a mixed solution containing ethylenediamine and methanol, stirring for 0.5h at 0 ℃, then heating to 25 ℃ and continuously stirring for reaction for 96h, and distilling under reduced pressure after the reaction is finished to remove methanol and excessive ethylenediamine, thereby obtaining a product which is marked as G2.0;
(3) Preparing silica nanoparticles containing PAMAM dendrimers and mercapto groups: mixing G1.0 and 3-mercaptopropyl trimethoxy silane, magnetically stirring for 2 hours, adding deionized water, then dropwise adding ammonium fluoride solution, and stirring at 25 ℃ for reaction for 24 hours; aging at 40 ℃ for 48 hours, filtering and washing with deionized water to obtain white precipitate, performing Soxhlet extraction on the white precipitate with ethanol for 12 hours, and freeze-drying at-60 ℃ for 48 hours to obtain the silica nanoparticle containing the 1.0-generation PAMAM dendrimer and mercapto; then G1.0 is replaced by G2.0, and the silica nanoparticle containing the 2.0-generation PAMAM dendrimer and the sulfhydryl group is prepared by the identical operation;
(4) Preparing a PAMAM dendrimer and sulfhydryl-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel: combining PAMAM dendrimer and sulfhydryl-containing silica nanoparticles with CaCO 3 Dispersing the powder into sodium alginate solution by ultrasonic wave to obtain uniform suspension; then adding graphene oxide solution into the sodium alginate solution, stirring and carrying out ultrasonic treatment to further disperse the mixture for 20min, and then adding the glucono-delta-lactone solution under vigorous stirring; finally, the mixture is rapidly poured into a mould, and is kept stand for 30min to form wet gel, and the formed wet gel is placed at-60 DEG CAnd freeze-drying at the temperature of 48 hours to obtain the silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and sulfhydryl groups.
Further, the volume ratio of methyl acrylate to G0 in the step (1) is (1-1.1): 1.
Still further, the ratio of the mass of G0.5 to the volume of methanol in step (1) is 25g:30mL;
the volume ratio of ethylenediamine to methanol in the ethylenediamine and methanol mixed solution is 115mL to 120mL;
the dripping time is 4 hours.
Further, the mass ratio of the volume of the methyl acrylate to 1.0 in the step (2) is (18-19) mL:20g.
Still further, the ratio of the mass of G1.5 to the volume of methanol in step (2) is 12g:30mL;
the volume ratio of ethylenediamine to methanol in the ethylenediamine and methanol mixed solution is 50mL to 100mL;
the dripping time is 4 hours.
Further, the molar ratio of G1.0 to 3-mercaptopropyl trimethoxysilane in step (3) is (1-5): 1;
the molar ratio of the G2.0 to the 3-mercaptopropyl trimethoxysilane is (1-5): 1;
the concentration of the ammonium fluoride solution is 0.014/g/L;
the volume ratio of deionized water to ammonium fluoride solution is 5mL to 4.5mL.
Further, the PAMAM dendrimer-and mercapto-containing silica nanoparticles and CaCO in step (4) 3 The mass ratio of the powder is 0.20g to 0.17g;
the mass ratio of the PAMAM dendrimer-containing and sulfhydryl-containing silicon dioxide nano-particles to sodium alginate is 0.20 g/0.75 g;
the mass ratio of the PAMAM dendrimer-containing and mercapto-containing silicon dioxide nanoparticles to graphene oxide is 0.20g to 0.06g;
the mass ratio of the PAMAM dendrimer and mercapto-containing silica nanoparticles to the glucono-delta-lactone is 0.20g to 0.30g.
The invention also provides application of the PAMAM dendrimer and mercapto-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel prepared by the method in adsorption treatment of Cd (II) or CV (nitrogen-containing organic dye).
Compared with the composite aerogel prepared by the pure silica nanoparticles, sodium alginate and graphene oxide, the aerogel prepared by the method has the advantages of more abundant functional groups and more content, can be suitable for adsorption separation of various pollutants such as metal ions, dyes and the like, and has obviously improved adsorption quantity. For example, compared with the pure silica/sodium alginate/graphene oxide composite aerogel, the adsorption amounts of the silica/sodium alginate/graphene oxide composite aerogel containing PAMAM dendrimer on Cd (II), ag (I), hg (II) and Pb (II) are respectively 0.67, 0.40, 0.27 and 0.26 mmol/g, and the adsorption amounts of the silica/sodium alginate/graphene oxide composite aerogel on the four metal ions are respectively improved by 5.09, 2.07, 12.50 and 25.00 times; the adsorption amounts of the PAMAM dendrimer-containing silicon dioxide/sodium alginate/graphene oxide composite aerogel on crystal violet, basic fuchsin, malachite green and methyl orange are 695.05, 689.78, 645.58 and 295.31 mg/g respectively, and compared with the adsorption amounts of the pure silicon dioxide/sodium alginate/graphene oxide composite aerogel on the four dyes, the adsorption amounts of the pure silicon dioxide/sodium alginate/graphene oxide composite aerogel on the four dyes are respectively improved by 4.15, 4.28, 4.86 and 1.92 times.
Drawings
FIG. 1 is a comparison of the adsorption performance of a silica/sodium alginate/graphene oxide composite aerogel alone versus a silica/sodium alginate/graphene oxide composite aerogel containing PAMAM dendrimers on metal ions (a) and dyes (b);
FIG. 2 is an infrared spectrum (a) of G0-G2.0 and an infrared spectrum (b, G1.0-S-1/1/GO/SA (1), G1.0-S-1/3/GO/SA (2), G1.0-S-1/5/GO/SA (3), G2.0-S-1/1/GO/SA (4), G2.0-S-1/3/GO/SA (5) and G2.0-S-1/5/GO/SA (6)) of a series of silica composites;
FIG. 3 is a high resolution spectrum of N1S (b), S2 p (C), O1S (d), C1S (e) and Si 2p (f) of a series of silica composites with XPS spectra (a), G1.0-S-1/3/GO/SA;
FIG. 4 shows the thermogravimetric curves (a) and the mercury-removal curves for G1.0-S-1/3/GO/SA and the pore size distribution (b and c) of the silica composite;
FIG. 5 is a scanning electron microscope image of a silica composite aerogel (a-c is respectively G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA is amplified 50 times, d-f is respectively amplified 100 times, G-i is respectively G2.0-S-1/1/GO/SA, G2.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA is amplified 50 times, G-l is respectively amplified 100 times);
fig. 6 is a silica composite aerogel vs metal ion (a, c= 112.41mg·l -1 T=25 ℃) and dye (b, c=1000 mg·l -1 Adsorption performance study at t=25℃;
FIG. 7 shows the pH of the solution versus the adsorption of Cd (II) (a, C= 112.41 mg.L) -1 T=25 ℃) and CV (b, c=200mg·g -1 Influence of T=25℃, and adsorption of Cd (II) and CV (C-d, C) in binary system (Cd(Ⅱ)) =112.41mg·L -1 ，C (CV) =200mg·g -1 T=25℃);
FIG. 8 is a silica composite aerogel vs. Cd (II) (a, C= 112.41 mg.L) -1 T=25 ℃, ph=6) and CV (b, c=200mg·g -1 Kinetic profile of t=25 ℃, ph=6) for Cd (ii) and CV (C-d, C in binary system (Cd(Ⅱ)) =112.41mmol·L -1 ，C (CV) =200mg·g -1 T=25 ℃, ph=6);
FIG. 9 shows a silica composite aerogel vs. Cd (II) (a-b, C=56.21-449.64 mg.L) -1 T=25 ℃, ph=6) and CV (C-d, c=50-200 mg·g -1 T=25 ℃, ph=6);
FIG. 10 is the effect of initial concentration on Cd (II) (a) and CV (b) in a G1.0-S-1/3/GO/SA adsorption Cd (II) -CV binary system;
FIG. 11 is a graph of the infrared spectrum (a) before and after adsorption of Cd (II) and CV by G1.0-S-1/3/GO/SA, the XPS spectrum (b) and the high resolution spectra of O1S, N1S, S2 p (c-h);
FIG. 12 is a graph of G1.0-S-1/3/GO/SA regeneration performance;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and mercapto groups:
(1) Preparation G1.0: the 3-aminopropyl triethoxysilane is marked as G0, and the amino group is marked as N 2 Under the protection, 76.0 mL methyl acrylate and 70.0 mL of G0 are dissolved in methanol, stirred and reacted at 25 ℃ for 24h, and after the reaction is finished, the methanol and the superfluous methyl acrylate are removed by reduced pressure distillation to obtain a product which is marked as G0.5; 25.0 g of G0.5 was dissolved in 30mL of methanol at 0℃and N 2 Under the protection, slowly dripping the methanol solution of G0.5 into the mixed solution containing 115.0 mL ethylenediamine and 120.0 mL methanol in 4h, keeping stirring at 0 ℃ for 0.5h, then heating to 25 ℃ and continuing stirring for 96h reaction, and removing the methanol and the ethylenediamine through reduced pressure distillation after the reaction is finished to obtain a product which is marked as G1.0;
(2) Preparation G2.0: first, 18.8 g mL of methyl acrylate and 20.0 g of G1.0 are dissolved in methanol under N 2 Stirring at 0 ℃ under protection for 0.5h, then heating to 25 ℃ and continuing stirring for reaction for 24h, and removing methanol and redundant methyl acrylate by reduced pressure distillation after the reaction is finished to obtain a product which is marked as G1.5; dissolving 12.0 g G1.5 in 30mL methanol at 0deg.C with N 2 Under the protection, dripping the mixture into a solution containing 50.0 mL ethylenediamine and 100mL methanol in 4h, stirring at 0 ℃ for 0.5h, heating to 25 ℃ and continuing to stir for reaction for 96h, and distilling under reduced pressure after the reaction is finished to remove methanol and excessive ethylenediamine to obtain a product which is marked as G2.0;
the synthetic route of the step (1) and the step (2) is as follows:
(3) Preparing silica nanoparticles containing PAMAM dendrimers and mercapto groups: 8.66G (0.021 mol) of G1.0 and 1.37G (0.007 mol) of 3-mercaptopropyl trimethoxysilane are taken and mixed, 5mL deionized water is added by magnetic stirring 2h, then 4.5mL ammonium fluoride solution with the concentration of 0.014G/L is added dropwise and stirred at 25 ℃ for reaction 24h; aging at 40deg.C 48h, filtering, washing with deionized water to obtain white precipitate, soxhlet extracting with ethanol 12h, freeze drying at-60deg.C 48h to obtain product, denoted as G1.0-S-1/3;
(4) Preparing a PAMAM dendrimer and sulfhydryl-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel: 0.2 g of G1.0-S-1/3 and 0.17g of CaCO 3 Dispersing the powder into sodium alginate solution (0.75 g sodium alginate is dissolved in 30mL deionized water) by ultrasonic wave to obtain uniform suspension; then adding graphene oxide solution (0.06 g graphene oxide dispersed in 10 mL deionized water) into the sodium alginate solution, stirring and carrying out ultrasonic treatment to further disperse the mixture for 20min, and then adding glucono-delta-lactone solution (0.3 g glucono-delta-lactone dissolved in 10 mL deionized water) under vigorous stirring; and finally, rapidly pouring the mixture into a mould, standing for 30min to form wet gel, and freeze-drying the wet gel at-60 ℃ for 48h to obtain the prepared silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and sulfhydryl groups, wherein the G1.0-S-1/3/GO/SA is recorded.
Example 2
The preparation procedure is as in example 1, except that in step (3) G1.0 is used in an amount of 0.07mol, the product being designated G1.0-S-1/1; the product of the step (4) is marked as G1.0-S-1/1/GO/SA.
Example 3
The preparation procedure is as in example 1, except that in step (3) G1.0 is used in an amount of 0.35mol, the product being designated G1.0-S-1/5; the product of the step (4) is marked as G1.0-S-1/5/GO/SA.
Example 4
The preparation procedure is as in example 1, except that in step (3) G2.0 is used in an amount of 0.21mol, the product being designated G2.0-S-1/3; the product of the step (4) is marked as G2.0-S-1/3/GO/SA.
Example 5
The preparation procedure is as in example 4, except that in step (3) G2.0 is used in an amount of 0.07mol, the product being designated G2.0-S-1/1; the product of the step (4) is marked as G2.0-S-1/1/GO/SA.
Example 6
The preparation procedure is as in example 4, except that in step (3) G2.0 is used in an amount of 0.35mol, the product being designated G2.0-S-1/5; the product of the step (4) is marked as G2.0-S-1/5/GO/SA.
Test example 1
The adsorption performance of the pure silica/sodium alginate/graphene oxide composite aerogel and the PAMAM tree-shaped macromolecule-containing silica/sodium alginate/graphene oxide composite aerogel prepared in the embodiment 1 on metal ions and dyes are compared, and the results are shown in the figure 1, and show that the adsorption amounts of the PAMAM tree-shaped macromolecule-containing silica/sodium alginate/graphene oxide composite aerogel prepared in the invention on Cd (II), ag (I), hg (II) and Pb (II) are respectively 0.67, 0.40, 0.27 and 0.26 mmol/g, and compared with the adsorption amounts of the pure silica/sodium alginate/graphene oxide composite aerogel on the four metal ions, the adsorption amounts of the pure silica/sodium alginate/graphene oxide composite aerogel are respectively improved by 5.09, 2.07, 12.50 and 25.00 times; the adsorption amounts of the PAMAM dendrimer-containing silicon dioxide/sodium alginate/graphene oxide composite aerogel on crystal violet, basic fuchsin, malachite green and methyl orange are 695.05, 689.78, 645.58 and 295.31 mg/g respectively, and compared with the adsorption amounts of the pure silicon dioxide/sodium alginate/graphene oxide composite aerogel on the four dyes, the adsorption amounts of the pure silicon dioxide/sodium alginate/graphene oxide composite aerogel on the four dyes are respectively improved by 4.15, 4.28, 4.86 and 1.92 times.
Test example 2 characterization of silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and thiol groups
2.1 Infrared Spectrum
Preliminary characterization of the structure of G0.5-G2.0 by FTIR was performed, and the results are shown in FIG. 2 (a). For the infrared spectrum of G0, at 2953 cm -1 And 2819 cm -1 Symmetrical and asymmetrical stretching vibration peaks of methyl and methylene appear at 3293 cm -1 NH is present at 2 Is not shown in the figure). After reaction of G0 with methyl acrylate, in FTIR spectrum of G0.5, NH 2 The absorption peak of (C) disappeared at 1743 cm -1 At which a characteristic absorption peak of carbonyl group (c=o) appears, indicating successful synthesis of G0.5. After reaction of G0.5 with ethylenediamine, the absorption peak of carbonyl group disappeared in the infrared spectrum of G1.0 at 1657 cm -1 And 1556 cm -1 An absorption peak of the amide appears, which indicates successful synthesis of G1.0. The infrared spectra of G1.5 and G2.0 are similar to those of G0.5 and G1, which shows that G0.5-G2.0 is successfully synthesized by a divergent synthesis method.
The infrared spectrum of the silica/sodium alginate/graphene oxide composite material containing PAMAM dendrimer and mercapto is shown in (b) of FIG. 2, 3284cm in G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA -1 The broad absorption band appearing at this point is of the same kind as OH and NH 2 Is stretched out and stretched out; 2924 cm -1 And 2840 cm -1 Absorption peak at CH 2 Asymmetric and symmetric telescopic vibration absorption peaks of (a); 2600 cm -1 A telescopic vibration absorption peak of SH is nearby; 1598 cm -1 And 1400 cm -1 The absorption peaks at the positions are respectively symmetrical and asymmetrical stretching vibration peaks of COOH; 1030 cm -1 The asymmetric stretching vibration peak of Si-O-Si is shown. The infrared spectra of G2.0-S-1/1/GO/SA, G2.0-S-1/3/GO/SA and G2.0-S-1/5/GO/SA are similar to those of G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA and G1.0-S-1/5/GO/SA. The analysis initially shows that the series of PAMAM dendrimer-containing silicon dioxide/sodium alginate/graphene oxide composite materials are successfully synthesized.
2.2X-ray photoelectron spectroscopy
The structure of the materials prepared in examples 1-6 was further characterized by XPS and the results are shown in FIG. 3. In FIG. 3 (a), characteristic peaks of C, O, S, N, si, ca and Na are observed in the high-resolution spectra of all composite aerogels, which indicates that PAMAM dendrimer and mercapto group-containing silica nanoparticles and seaweedAnd compounding the sodium acid and the graphene oxide successfully. Taking G1.0-S-1/3/GO/SA as an example, the spectrum of the series composite material is further analyzed by a high-resolution XPS spectrum, N1S and S2 p high-resolution spectra are shown as (b) in FIG. 3 and (c) in FIG. 3, and characteristic peaks at 400.00 eV and 399.25 eV in the N1S high-resolution spectrum are attributed to NH 2 And C-N; in the high resolution spectrum of S2 p, the characteristic peaks of 163.44 eV and 164.50 eV are assigned to S2 p 3/2 And S2 p 1/2 . The high resolution spectra of O1 s in fig. 3 (d), characteristic peaks 532.57 eV and 531.50 eV demonstrate the presence of OH and COOH in sodium alginate and c=o in graphene oxide. FIG. 3 (e) is a high resolution spectrum of C1 s, C-C/CH 3 Characteristic peaks for C-Si and C-O appear at 284.70, 286.35 and 288.12 eV, respectively. The high resolution spectrum of Si 2p in (f) of fig. 3 shows a characteristic peak at 102.18 eV. XPS results further indicate that the preparation of the silica/graphene oxide/sodium alginate composite material containing PAMAM dendrimers and sulfhydryl groups is successful.
2.3 thermogravimetric analysis
The thermal stability of the composite aerogel was measured by TGA and the results are shown in (a) of fig. 4. The prepared composite aerogel has a similar thermal weight curve, and the thermal weight loss is mainly divided into three stages. Taking G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA as examples, the first stage thermal weight loss is in the range of 25 ℃ to 150 ℃ due to evaporation of water molecules physically adsorbed by the device. The second stage of thermal weight loss occurs in the range of 200 ℃ to 300 ℃ due to the cleavage of hydrogen bonds between sodium alginate, graphene oxide, silica and dehydroxylation of sodium alginate and preliminary degradation of sodium alginate. In the range of 350 ℃ to 800 ℃, the third stage of thermal weight loss occurs due to further degradation of sodium alginate and carbonization of graphene oxide and decomposition of the silica surface functional groups. The final thermal weight loss rates of G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA, G2.0-S-1/1/GO/SA, G2.0-S-1/3/GO/SA and G2.0-S-1/5/GO/SA were 68.39%, 79.83%, 80.94%, 72.46%, 70.84% and 71.97%. The TGA result shows that the prepared composite aerogel has good thermal stability and can be applied in a wider temperature range below 200 ℃.
2.4 pore size analysis
Using G1.0-S-1/3/GO/SA as an example, the range of various pore structures in the composite material was measured by mercury intrusion, and the results are shown in FIG. 4 (b and c). The porosity of G1.0-S-1/3/GO/SA can reach 92.03%, and as can be seen from (b) of FIG. 4, the cumulative injection amount of mercury increases sharply with increasing pressure, which indicates that the first stage is mainly a macroporous structure, and mercury fills the pore volume between aerogels. In the second phase, as the pressure increases, the quantity of mercury injected does not substantially increase, and the energy consumption is mainly represented by the material itself absorbing most of the energy, the volume being further compressed. On the other hand, the capillary and mesopores contained in the composite material are also filled with mercury under high pressure. The pore size distribution is shown in (c) of FIG. 4, and the composite aerogel has two pore structures, wherein the average pore size is 60.72 μm and 24.21 μm respectively, and the main pore structure is mainly a macroporous structure of about 24 μm.
2.4 scanning electron microscope analysis
Characterization of the surface morphology of the prepared composite aerogels by SEM, FIG. 5 shows SEM pictures of G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA, G2.0-S-1/1/GO/SA, G2.0-S-1/3/GO/SA and G1.0-S-1/5/GO/SA, and it can be seen from the figures that the prepared composite aerogel has a typical aerogel structure, the pore structures of which are similar and all consist of pores similar to the circular structure. For G1.0-S-1/1/GO/SA, G1.0-S-1/3/GO/SA, G1.0-S-1/5/GO/SA, the pore diameter gradually increases as the proportion of PAMAM dendrimers increases; in addition, as the algebra of the PAMAM dendrimer increases, the pore size of the prepared silica composite aerogel tends to increase.
Test example 3
Adsorption performance research of PAMAM dendrimer and sulfhydryl-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel on Cd (II) and CV
3.1 static adsorption
The prepared series of aerogel has the characteristics of Cd (II), ag (I), pb (II) and Hg (II)Adsorption performance, the results are shown in fig. 6 (a). The adsorption capacity of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA to Cd (II) is obviously better than that of other metal ions. For example, the adsorption amount of G1.0-S-1/3/GO/SA to Cd (II) is 75.31 mg. Multidot.g -1 Under the same experimental conditions, the adsorption amounts of the catalyst are 1.74 times, 1.80 times and 4.68 times of the adsorption amounts of the catalyst on Ag (I), pb (II) and Hg (II), respectively. The remarkable binding capacity of PAMAM dendrimers to Cd (ii) is a major contributor to their adsorption properties. The adsorption performance results of the series of silica composite aerogels on CV, FB, MG, MO and other dyes are shown in (b) of fig. 6, and the adsorption performance of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA on CV are superior to those of other dyes. The adsorption capacity of G1.0-S-1/3/GO/SA to CV is 636.84 mg G -1 The adsorption amount of CV was 1.00, 1.71 and 2.51 times that of FB, MG and MO, respectively. As SA/GO/G1.0-S-1/3 and SA/GO/G2.0-S-1/3 have good adsorption separation capability on Cd (II) and CV, the subsequent experiments will be represented by the two, and the factors and rules affecting the adsorption separation performance are systematically researched.
3.2 influence of the pH of the solution on the adsorption of Cd (II) and CV
The influence of the pH of the solution on the adsorption performance of Cd (II) or CV in a single system and the influence of the pH of the solution on the adsorption performance of Cd (II) and CV in a Cd (II) -CV binary system are studied. The effect of the solution pH on the adsorption of Cd (II) by G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA in a single solution system is shown in (a) of FIG. 7, the adsorption amount of Cd (II) is greatly influenced by the solution pH, the adsorption amount increases with the increase of the solution pH, and the adsorption amount reaches the maximum value at the pH of 6. When the pH of the solution is 1, the adsorption amounts of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA to Cd (II) are 1.12 and 4. mg.g respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the When the pH is 6, the adsorption capacity of Cd (II) is 67.45 and 56.21 mg g -1 5922% and 1149% respectively. At low pH values of the solution, a large amount of H is present in the solution + The functional group is protonated and positively charged to be in contact with Cd 2+ Generating electrostatic repulsive action, resulting in small adsorption quantity; h as the pH of the solution increases + The concentration is reduced, the protonation degree of the functional groups is reduced, the electrostatic repulsive effect is reduced, and the adsorption amount is increased.
Solution pH to single solution SystemThe effect of CV adsorption performance is shown in FIG. 7 (b). The adsorption amount of the synthesized silica composite aerogel to CV also increases with the increase of the pH value of the solution, reaching the maximum adsorption amount at ph=10. When the pH of the solution is 1, the adsorption amounts of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA to CV are respectively 10.12 and 2.80 mg G -1 The method comprises the steps of carrying out a first treatment on the surface of the At pH 10, the adsorption amounts to CV were 204.80 and 175.77 mg. G, respectively -1 20.24 times and 62.78 times the adsorption capacity at pH 1, respectively. This is mainly because at low solution pH, the functional groups on the aerogel surface become protonated and positively charged, and electrostatic repulsion with CV molecules prevents adsorption, and as the solution pH increases, the number of active functional groups available for adsorption increases, and thus the amount of adsorption increases.
Taking G1.0-S-1/3/GO/SA as a typical representative, the influence of the pH of the solution on the adsorption of Cd (II) and CV in a Cd (II) -CV binary system is further examined, and the pH is selected to be in the range of 1-6 because the Cd (II) is gradually hydrolyzed and is unfavorable for adsorption when the pH is more than 6, and the result is shown in (c and d) in FIG. 7. The effect of the pH of the solution on the adsorption of Cd (II) and CV in a Cd (II) -CV binary system is similar to that of a single system, the adsorption amount of Cd (II) and CV increases with the increase of the pH value of the solution, and when the pH of the solution is 1, the adsorption amount of G1.0-S-1/3/GO/SA on Cd (II) and CV is 1.14 and 10.12 mg G respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the The adsorption capacity of Cd (II) and CV was 62.59 and 192.80 mg g when the pH of the solution was 6 -1 5390.35% and 1805.14% are added respectively. The adsorption amounts of the synthesized silicon dioxide composite aerogel to Cd (II) and CV reach the maximum value at the pH value of 6, and the maximum adsorption amounts are 62.59 and 192.80 mg g respectively -1 Compared with a single pollutant system, the maximum adsorption amount of Cd (II) and CV of the synthesized silicon dioxide composite aerogel is reduced by 7.21 percent and 5.86 percent respectively.
3.3 adsorption kinetics for Cd (II) and CV
The adsorption kinetics curves of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA on Cd (II) and CV are shown as (a and b) in FIG. 8, the adsorption rate on Cd (II) is higher in the first 100 min, and the adsorption amounts can reach 69.69 and 56.21 mg G respectively -1 96.88% and 87% of the adsorption amount at equilibrium.72%. Subsequently, the adsorption rate gradually decreased until 150 min adsorption reached equilibrium, the equilibrium adsorption capacities were 71.94 and 64.07 mg g, respectively -1 . FIG. 8 (b) shows adsorption kinetics curves of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA for CVs, which are also fast in the first 100 min, with adsorption capacities of 185.24 and 156.28 mg G -1 Accounting for 86.44% and 88.80% of the adsorption capacity at equilibrium, respectively. The adsorption rate was then gradually decreased, an adsorption equilibrium was reached at 120 min, and equilibrium adsorption capacities were 214.30 and 176.22 mg g, respectively -1 . The adsorption speed is high in the initial stage of adsorption, and the aerogel can rapidly adsorb Cd (II) and CV due to the fact that the surface of the silicon dioxide composite aerogel contains rich adsorption sites and the concentration of Cd (II) or CV in the solution is high; as adsorption proceeds, the available adsorption sites on the aerogel surface and the concentration of contaminants in the solution gradually decrease, resulting in a decrease in the adsorption rate until an adsorption equilibrium is reached.
Further represented by G1.0-S-1/3/GO/SA, the adsorption kinetics of the synthesized silica composite aerogel on Cd (II) and CV in binary systems were studied, and the results are shown in FIG. 8 (c and d). In a binary system of Cd (II) -CV, the adsorption trend of G1.0-S-1/3/GO/SA on the Cd (II) and CV is consistent with that of a single pollutant system, the adsorption equilibrium is reached on the Cd (II) and CV at 120 min, and the equilibrium adsorption amounts are 50.58 and 182.30 mg G respectively -1 . Compared with the equilibrium adsorption quantity of G1.0-S-1/3/GO/SA to Cd (II) and CV in a monobasic system, the equilibrium adsorption quantity is respectively reduced by 27.42 percent and 14.93 percent.
3.4 adsorption thermodynamics on Cd (II) and CV
Isothermal adsorption lines of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA for Cd (II) at different temperatures are shown in FIG. 9 (a and b). As shown in the figure, increasing the initial concentration of Cd (II) can obviously promote the adsorption of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA to Cd (II). For example, at 35℃when the Cd (II) concentration increases from 56.21 to 449.64 mg.L -1 At the time of the reaction, the adsorption amounts of the Cd (II) by the G1.0-S-1/3/GO/SA and the G2.0-S-1/3/GO/SA are increased from 96.67 and 88.80 to 219.20 and 179.86 mg.g respectively -1 . The increase in temperature also promotes the adsorption of Cd (II). For example, the number of the cells to be processed,at a concentration of 449.64 mg.L -1 The adsorption amounts of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA to Cd (II) at 15 ℃ are 145.01 and 148.38 mg.g respectively -1 . When the adsorption temperature is raised to 35 ℃, the adsorption capacity of Cd (II) is 219.20 and 179.86 mg g -1 The temperature is increased by 51.16 percent and 21.21 percent compared with the temperature at 15 ℃. The adsorption of CV is similar to that of CV. At 35℃when the initial CV concentration was increased from 500 to 2500 mg.L -1 At the time of CV adsorption, the adsorption amounts of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA are respectively from 110.24 and 33.60 mg G -1 To 190.25 and 105.73 mg g -1 . The increase in temperature also promotes adsorption to the CV. For example, at a concentration of 500 mg.L -1 The adsorption amounts of G1.0-S-1/3/GO/SA and G2.0-S-1/3/GO/SA to CV at 15 ℃ are 70.27 and 16.57 mg G respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the When the adsorption temperature is increased to 35 ℃, the adsorption quantity of the G1.0-S-1/3/GO/SA and the G2.0-S-1/3/GO/SA to CV is increased to 110.24 and 33.60 mg.g -1 The temperature is increased by 56.88% and 102.78% compared with the temperature at 15 ℃. The concentration increase can improve the adsorption performance mainly because more Cd (II) or CV molecules exist at high concentration, which is favorable for the interaction with the functional groups on the surface of the composite aerogel to be adsorbed, so that the adsorption balance moves rightwards, and the adsorption quantity is increased; the positive effect of temperature on adsorption indicates that the adsorption process is an endothermic process.
The effect of the initial concentrations of Cd (II) and CV in the binary Cd (II) -CV system on the adsorption of Cd (II) and CV was further studied on the basis of G1.0-S-1/3/GO/SA, and the results are shown in FIG. 10. Under the condition that the initial concentration of Cd (II) is constant, the adsorption quantity of G1.0-S-1/3/GO/SA to Cd (II) is reduced along with the increase of CV concentration. For example, the concentration of Cd (II) in the Cd (II) -CV binary system is 449.64 mg.L -1 In the absence of CV, the adsorption amount of G1.0-S-1/3/GO/SA to Cd (II) was 175.67 mg. G -1 The method comprises the steps of carrying out a first treatment on the surface of the When the CV concentration increases to 2500 mg.L -1 When the adsorption capacity of the catalyst to Cd (II) is 100.04 mg g -1 The reduction is 43.05 percent. Similarly, the adsorption amount of G1.0-S-1/3/GO/SA to CV decreases with increasing concentration of Cd (II) under the condition that the initial concentration of CV is constant. For example, the concentration of CV in the Cd (II) -CV binary system is 500 mg.L -1 In the absence of Cd (II), the adsorption amount of G1.0-S-1/3/GO/SA to CV is 100.37 mg G -1 The method comprises the steps of carrying out a first treatment on the surface of the When the concentration of Cd (II) is increased to 449.64 mg.L -1 The adsorption amount of CV was 32.56 mg g -1 67.56% reduction, which indicates that there is competitive adsorption of Cd (II) and CV adsorption processes.
3.5 adsorption mechanism for Cd (II) and CV
The mechanism of adsorption of Cd (II) and CV to the composite aerogel was investigated by FTIR and XPS. Taking G1.0-S-1/3/GO/SA as an example, the FTIR and XPS spectra before and after adsorption of Cd (II) and CV are shown in FIG. 11. In FIG. 11 (a), OH in the G1.0-S-1/3/GO/SA IR spectrum was at 3284cm -1 The absorption peaks in the vicinity are obviously weakened after adsorbing Cd (II) and CV, which indicates that OH participates in the adsorption process of Cd (II) and CV; COOH at 1598 and 1598 cm -1 The symmetrical stretching vibration peak of (C) is also weakened, which indicates that COOH also participates in the adsorption process of Cd (II) and CV. Due to NH 2 The absorption peak of (2) overlaps with the absorption peak of OH, and NH cannot be accurately determined 2 Whether to participate in the adsorption process. Therefore, the adsorption mechanism is further revealed by XPS. The XPS spectra before and after the adsorption of G1.0-S-1/3/GO/SA are shown in (b) of FIG. 11, and in the XPS spectrum after the adsorption of Cd (II), a characteristic peak of Cd 3d is observed at 401.22 eV, which indicates that Cd (II) is adsorbed by G1.0-S-1/3/GO/SA; for XPS spectra of G1.0-S-1/3/GO/SA after adsorption of CV, a characteristic peak enhancement of N1S was observed at 400.00 eV due to nitrogen element contained in CV, which indicates that CV was adsorbed by G1.0-S-1/3/GO/SA. After adsorption of Cd (ii), the characteristic peaks of OH/COOH and c=o in the high-resolution spectra of O1 s shifted from 532.57, 531.50 eV to 532.60, 531.75 eV, and after adsorption of CV to 532.68 and 531.80 eV. After adsorption of Cd (II), C-N and NH in the high resolution spectra of N1s 2 The characteristic peaks of (3) move from 399.25 and 400.00 eV to 399.75 and 400.01 eV, and after adsorption CV move to 399.35 and 400.30 eV. Similarly, after adsorption of Cd (II), S2 p in the high resolution spectrum of S2 p 1/2 And S2 p 3/2 The characteristic peaks of (3) move from 164.50 and 163.44 eV to 164.60 and 163.50 eV, and after adsorption CV to 164.40 and 163.30 eV. XPS results showed that O-H, COOH, C= O, NH 2 C-N and SH and other functional groups participate in the adsorption process of Cd (II) and CV.
3.6 cyclic regeneration and use properties of PAMAM dendrimer and mercapto-containing silica/graphene oxide/sodium alginate composite aerogel
G1.0-S-1/3/GO/SA is selected as representative for researching the cyclic regeneration service performance of the synthesized series of silicon dioxide composite aerogel. Respectively 1mol ∙ L -1 HNO 3 The aerogel after adsorbing Cd (II) and CV was regenerated by using 5% thiourea solution and absolute ethanol as eluent, and the results are shown in FIG. 12. As can be seen from the graph, after the first adsorption of Cd (II) and CV, the regeneration rates of G1.0-S-1/3/GO/SA were 96.62% and 96.34%, respectively. After the second and third adsorption-desorption cycles, the regeneration rate of G1.0-S-1/3/GO/SA was slightly decreased, the regeneration rates after adsorption of Cd (II) were 95.10% and 94.86%, respectively, and the regeneration rates after adsorption of CV were 95.82% and 94.48%, respectively. After five adsorption-desorption cycles, the regeneration rate of the G1.0-S-1/3/GO/SA after adsorbing Cd (II) and CV can still be maintained at 90.89% and 90.41%. The result shows that the prepared silicon dioxide composite aerogel has good recycling performance.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (8)
1. The preparation method of the silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and mercapto groups is characterized by comprising the following steps:
(1) Preparation G1.0: the 3-aminopropyl triethoxysilane is marked as G0, and the amino group is marked as N 2 Under the protection, dissolving methyl acrylate and G0 in methanol, stirring at 25 ℃ for reaction for 24 hours, and distilling under reduced pressure to remove methanol and redundant methyl acrylate after the reaction is completed, so as to obtain a product, namely G0.5; dissolving G0.5 in methanol at 0deg.C with N 2 Under the protection, the methanol solution of G0.5 is dripped into the mixed solution containing ethylenediamine and methanol, and the temperature is kept at 0 ℃ and stirredStirring for 0.5h, heating to 25 ℃, continuously stirring and reacting for 96h, and removing methanol and ethylenediamine through reduced pressure distillation after the reaction is finished to obtain a product which is marked as G1.0;
(2) Preparation G2.0: methyl acrylate and G1.0 were first dissolved in methanol at N 2 Stirring for 0.5h at 0 ℃ under protection, then heating to 25 ℃ and continuing stirring for reaction for 24h, and removing methanol and redundant methyl acrylate by reduced pressure distillation after the reaction is finished to obtain a product which is marked as G1.5; dissolving G1.5 in methanol at 0deg.C, N 2 Under the protection, dripping the mixture into a mixed solution containing ethylenediamine and methanol, stirring for 0.5h at 0 ℃, then heating to 25 ℃ and continuously stirring for reaction for 96h, and distilling under reduced pressure after the reaction is finished to remove methanol and excessive ethylenediamine, thereby obtaining a product which is marked as G2.0;
(3) Preparing silica nanoparticles containing PAMAM dendrimers and mercapto groups: mixing G1.0 and 3-mercaptopropyl trimethoxy silane, wherein the molar ratio of the G1.0 to the 3-mercaptopropyl trimethoxy silane is (1-5): 1; magnetically stirring for 2 hours, adding deionized water, then dropwise adding ammonium fluoride solution, and stirring at 25 ℃ for reaction for 24 hours; aging at 40 ℃ for 48 hours, filtering and washing with deionized water to obtain white precipitate, performing Soxhlet extraction on the white precipitate with ethanol for 12 hours, and freeze-drying at-60 ℃ for 48 hours to obtain the silica nanoparticle containing the 1.0-generation PAMAM dendrimer and mercapto; then G1.0 is replaced by G2.0, and the silica nanoparticle containing the 2.0-generation PAMAM dendrimer and the sulfhydryl group is prepared by the identical operation; the molar ratio of the G2.0 to the 3-mercaptopropyl trimethoxysilane is (1-5): 1;
(4) Preparing a PAMAM dendrimer and sulfhydryl-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel: combining PAMAM dendrimer and sulfhydryl-containing silica nanoparticles with CaCO 3 Dispersing the powder into sodium alginate solution by ultrasonic wave to obtain uniform suspension; then adding graphene oxide solution into the sodium alginate solution, stirring and carrying out ultrasonic treatment to further disperse the mixture for 20min, and then adding the glucono-delta-lactone solution under vigorous stirring; finally, the mixture is rapidly poured into a mould, and is kept stand for 30min to form wet gel, and the formed wet gel is placed at-60 DEG CAnd (3) performing freeze drying for 48 hours at the temperature to obtain the silica/graphene oxide/sodium alginate composite aerogel containing PAMAM dendrimers and sulfhydryl groups.
2. The preparation method of the PAMAM dendrimer and mercapto group-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel according to claim 1, wherein the volume ratio of methyl acrylate to G0 in the step (1) is (1-1.1): 1.
3. The preparation method of the PAMAM dendrimer and mercapto group-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel according to claim 2, wherein the volume ratio of the mass of G0.5 to the volume of methanol in the step (1) is 25g:30mL;
the volume ratio of ethylenediamine to methanol in the ethylenediamine and methanol mixed solution is 115mL to 120mL;
the dropping time was 4 hours.
4. The preparation method of the PAMAM dendrimer and mercapto group-containing silicon dioxide/graphene oxide/sodium alginate composite aerogel according to claim 1, wherein the mass ratio of the volume of the methyl acrylate to G1.0 in the step (2) is (18-19) mL to 20G.
5. The method of claim 4, wherein the ratio of the mass of G1.5 to the volume of methanol in step (2) is 12G/30 mL;
the volume ratio of ethylenediamine to methanol in the ethylenediamine and methanol mixed solution is 50mL to 100mL;
the dropping time was 4 hours.
6. The method for preparing the PAMAM dendrimer-and-mercapto-containing silica/graphene oxide/sodium alginate composite aerogel according to claim 1, wherein the concentration of the ammonium fluoride solution in the step (3) is 0.014/g/L;
the volume ratio of deionized water to ammonium fluoride solution is 5mL to 4.5mL.
7. The method for preparing the PAMAM dendrimer and mercapto group-containing silica/graphene oxide/sodium alginate composite aerogel according to claim 1, wherein the PAMAM dendrimer and mercapto group-containing silica nanoparticles and CaCO in the step (4) 3 The mass ratio of the powder is 0.20g to 0.17g;
the mass ratio of the PAMAM dendrimer-containing and sulfhydryl-containing silicon dioxide nano-particles to sodium alginate is 0.20 g/0.75 g;
the mass ratio of the PAMAM dendrimer-containing and mercapto-containing silicon dioxide nanoparticles to graphene oxide is 0.20g to 0.06g;
the mass ratio of the PAMAM dendrimer and mercapto-containing silica nanoparticles to the glucono-delta-lactone is 0.20g to 0.30g.
8. The use of a PAMAM dendrimer and thiol-containing silica/graphene oxide/sodium alginate composite aerogel prepared according to the method of any one of claims 1-7 in adsorption treatment of divalent chromium or nitrogen-containing organic dyes.
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| CN102161758A (en) * | 2011-01-26 | 2011-08-24 | 大连理工大学 | Preparation method of novel silica gel-based hyperbranched PAMAM (polyamidoamine) chelating resin |
| CN108654579A (en) * | 2018-05-17 | 2018-10-16 | 江苏大学 | A kind of preparation method of sodium alginate/cattail/graphene oxide composite aerogel |
| CN110026248A (en) * | 2019-05-06 | 2019-07-19 | 河北科技大学 | The method and application of a kind of catalyst, the catalyst preparation aeroge adsorbent material |
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