CN112316903A - One-step solvothermal preparation method and application of carbon fiber @ MAL hydrotalcite composite film - Google Patents
One-step solvothermal preparation method and application of carbon fiber @ MAL hydrotalcite composite film Download PDFInfo
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- CN112316903A CN112316903A CN202011136624.8A CN202011136624A CN112316903A CN 112316903 A CN112316903 A CN 112316903A CN 202011136624 A CN202011136624 A CN 202011136624A CN 112316903 A CN112316903 A CN 112316903A
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- carbon fiber
- composite film
- hydrotalcite
- mal
- hydrotalcite composite
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 171
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 170
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 170
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 135
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 54
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 45
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004202 carbamide Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910020068 MgAl Inorganic materials 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 159000000003 magnesium salts Chemical group 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 50
- 239000004917 carbon fiber Substances 0.000 abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 30
- 239000002243 precursor Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004729 solvothermal method Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000002441 X-ray diffraction Methods 0.000 description 25
- 239000012046 mixed solvent Substances 0.000 description 13
- 238000011065 in-situ storage Methods 0.000 description 11
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910000943 NiAl Inorganic materials 0.000 description 9
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 9
- 229910002515 CoAl Inorganic materials 0.000 description 7
- 229910052564 epsomite Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910018565 CuAl Inorganic materials 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000000777 hematopoietic system Anatomy 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a one-step solvothermal preparation method and application of a carbon fiber @ MAL hydrotalcite composite film. The preparation process of the composite film is as follows: pretreating carbon paper, and then adding divalent metal salt and Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of alcohol and water to obtain a hydrotalcite precursor; stirring, transferring to a reaction kettle, adding carbon paper, and preparing the composite film by adopting a solvothermal method. The invention improves the hydrophilicity of the carbon paper by adding alcohol, so that the MAL hydrotalcite can grow on the carbon fiber, thereby improving the growth rate of the MAL hydrotalciteThe bonding strength between the carbon fiber and the MAL hydrotalcite is improved, the adsorption effect of the composite film on heavy metal ions is improved, the adsorption capacity of the composite film on Pb (II) under a certain condition is 11.5mg/g, the adsorption rate is 99.8%, and the residual concentration of Pb (II) in the solution after adsorption is 0.04 mg/L.
Description
Technical Field
The invention belongs to the technical field of synthesis of composite materials, and particularly relates to a one-step solvothermal preparation method and application of a carbon fiber @ MAL hydrotalcite composite film.
Background
Contamination of heavy metal ions has been a serious problem over the past decades due to their high toxicity, carcinogenicity and non-degradability. Taking Pb (II) in mining, electroplating and lead battery industrial wastewater as an example, it can damage the nervous and hematopoietic systems of living beings. Therefore, toxic Pb (ii) ions must be removed from the wastewater before the above-mentioned wastewater is discharged. Among methods for removing heavy metal ions such as a chemical precipitation method, an ion exchange method, a membrane separation method, an adsorption method and the like, the adsorption method has the advantages of simplicity and convenience in operation, high selectivity, strong universality and the like, and particularly can effectively purify low-concentration heavy metal ion wastewater. Among these, adsorbents are key factors in determining the efficiency of adsorption processes.
Hydrotalcites, also known as Layered Double Hydroxides (LDHs), are generally of chemical composition
Wherein M is2+、M3+Are respectively divalent and trivalent metal cations, An-Is interlayer anion, and the hydrotalcite has the characteristics of interlayer ion exchangeability, higher surface area, memory effect and the like, is simple to synthesize, has low cost, and is widely applied to the field of adsorption. For example, CN109012573A discloses a method for adsorbing Cr (vi) by baking a magnesium aluminum hydrotalcite thin film, which has an adsorption amount of 46.38mg/g for Cr (vi) and an adsorption rate of 99%, but has a defect of too low strength.
Carbon fibers have good physical strength, and have the advantages of good chemical stability, high specific surface area and easiness in separation in an acidic or alkaline solution, so researchers try to compound the carbon fibers with hydrotalcite. For example, CN109289772A adopts a coprecipitation method to generate a lanthanum-doped hydrotalcite layer in situ on the wall of a multi-walled carbon nanotube, and then uses a cationic surfactant, namely cetyl pyridinium bromide to modify the surface of the hydrotalcite layer, and the modified hydrotalcite layer is used for adsorbing nitrate nitrogen, wherein the adsorption rate of the composite material prepared in a better state on the nitrate nitrogen reaches 99.5%. Peng et al (Peng X M, Wang M, Hu F P, et al. Multipath purification of theoretical CuAl layred double hydroxide/carbon fiber composites for the degradation of ammonia nitrogen [ J ]. Journal of Environmental Management,2018,220: 173. 182.) grow CuAl hydrotalcite on biomass carbon fiber by hydrothermal method and use it for adsorption of azo dyes with a maximum adsorption rate of 99.28%. CN110665483A is firstly adhered with a dopamine hydrochloride film on the surface of carbon paper, then MgAl hydrotalcite is grown by a hydrothermal method, the adsorption rate of the MgAl hydrotalcite on Pb (II) reaches 99.65%, and the residual concentration of the Pb (II) after adsorption is 0.07 mg/L. However, the preparation process is complex, a layer of polydopamine film needs to be adhered to the carbon paper, and the raw material of the high-price polydopamine hydrochloride is involved.
Disclosure of Invention
In order to solve the problems that carbon fibers are difficult to combine with hydrotalcite and the hydrotalcite is not uniformly distributed on the carbon fibers due to poor hydrophilicity of carbon paper in the prior art, the invention aims to provide a preparation method of a carbon fiber @ MAL hydrotalcite composite film, so that the hydrotalcite is firmly and uniformly combined on the surfaces of the carbon fibers.
The invention also aims to provide a carbon fiber @ MAL hydrotalcite composite film prepared by the method.
The invention further aims to provide application of the carbon fiber @ MAL hydrotalcite composite film.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a carbon fiber @ MAL hydrotalcite composite film comprises the following steps:
(1) cleaning and drying the carbon paper for later use;
(2) weighing divalent metal salt and Al2(SO4)3·18H2Dissolving O and urea in mixed solution of alcohol and water, wherein divalent metal salt is magnesium salt, nickel salt, cobalt salt or zinc salt, urea and water
The ratio of the amounts of substances of (a) to (b) is 8: 1, divalent metal ion and trivalent metal ion Al3+The ratio of the amounts of the substances (A) to (B) is 2-4: 1; uniformly stirring the obtained solution, transferring the solution into a hydrothermal reaction kettle, and putting the carbon paper treated in the step (1) into the solution; and (2) sealing the hydrothermal reaction kettle, then carrying out hydrothermal reaction, naturally cooling to room temperature after the reaction is completed, washing the carbon paper with water until no white solid is on the surface of the carbon paper, and then drying to obtain the carbon fiber @ MAL hydrotalcite composite film (M ═ Mg, Ni, Co or Zn).
In the step (1), the carbon paper is sequentially subjected to ultrasonic treatment in acetone, ethanol and water, and then dried.
Preferably, the carbon paper is subjected to ultrasonic treatment in acetone, ethanol and water for 10min respectively, and the ultrasonic power is 180W.
Amount of the divalent metal salt substance in step (2): the volume of the mixed solution of alcohol and water was 0.00018 to 0.0036mol/50 mL.
The divalent metal ion and the trivalent metal ion Al in the step (2)3+The ratio of the amounts of substances (a) to (b) is preferably 3: 1.
the alcohol in the step (2) comprises any one of methanol, ethanol, n-propanol and isopropanol.
According to the invention, the hydrophilicity of the carbon paper is improved by adding alcohol, so that the MAL hydrotalcite can grow on the carbon fiber, the bonding strength between the carbon fiber and the MAL hydrotalcite is improved, and the adsorption effect of the composite film on heavy metal ions is improved.
The volume ratio of the alcohol in the mixed solution of the alcohol and the water in the step (2) is 10-60%.
The divalent metal salt in the step (2) includes one of magnesium sulfate, magnesium chloride, magnesium nitrate, zinc sulfate, zinc chloride, zinc nitrate, cobalt sulfate, cobalt chloride, cobalt nitrate, nickel sulfate, nickel chloride, nickel nitrate and the like.
In the step (2), the divalent metal salt is preferably a magnesium salt, and comprises at least one of magnesium sulfate, magnesium chloride and magnesium nitrate.
The temperature of the hydrothermal reaction in the step (2) is 90-150 ℃, and the time of the hydrothermal reaction is 10-24 h.
In the step (2), the obtained solution is stirred for 1h at 400r/min and then transferred into a reaction kettle with a polytetrafluoroethylene lining.
In a preferred scheme, the carbon fiber @ MgAl hydrotalcite composite film is prepared by the following steps:
(1) cleaning and drying the carbon paper for later use;
(2) weighing magnesium salt and Al2(SO4)3·18H2O and urea, and dissolving in a mixed solution of methanol and water, wherein the urea and the water
The ratio of the amounts of substances of (a) to (b) is 8: 1, divalent metal ion and trivalent metal ion Al3+The ratio of the amounts of substances of (a) to (b) is 3: 1, the volume ratio of methanol in the mixed solution of methanol and water is 60 percent; uniformly stirring the obtained solution, transferring the solution into a hydrothermal reaction kettle, and putting the carbon paper treated in the step (1) into the solution; and sealing the hydrothermal reaction kettle, carrying out hydrothermal reaction at 110 ℃ for 12h, naturally cooling to room temperature after the reaction is completed, washing the carbon paper with water until no white solid is on the surface of the carbon paper, and drying to obtain the carbon fiber @ MgAl hydrotalcite composite film.
The carbon fiber @ MAL hydrotalcite composite film can be used for adsorbing heavy metal ions, especially Pb (II), in an aqueous solution.
When the carbon fiber @ MAL hydrotalcite composite film prepared by the invention is used for removing heavy metal ions in an aqueous solution, the pH value of the aqueous solution containing heavy metal Pb (II) is adjusted to 6.0 by using 0.1mol/L NaOH solution.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method uniformly grows the hydrotalcite on the surface of the carbon fiber by a one-step solvothermal method, and has simple process and easy operation.
The carbon fiber @ MAL hydrotalcite composite film prepared by the invention is simple in separation operation after adsorbing heavy metal ions, and does not cause secondary pollution.
The carbon fiber @ MAL hydrotalcite composite film prepared by the invention has good adsorption effect on Pb (II). Under certain conditions, the adsorption capacity of the adsorbent to Pb (II) is 11.5mg/g, the adsorption rate is 99.8%, and the residual concentration of Pb (II) in the adsorbed solution is 0.04 mg/L.
Drawings
FIG. 1 is an SEM photograph of carbon fiber @ MgAl hydrotalcite composite films prepared from carbon paper (a) and examples 1-10 (b-k);
FIG. 2 is an XRD (X-ray diffraction) pattern of carbon paper and the carbon fiber @ MgAl hydrotalcite composite film prepared in examples 1 to 7, wherein b is a locally amplified XRD pattern;
FIG. 3 is an XRD (X-ray diffraction) pattern of the carbon fiber @ MAL hydrotalcite composite film prepared in examples 8-10, wherein b is a locally enlarged XRD pattern;
FIG. 4 is a graph showing the adsorption capacity of the carbon paper and the carbon fiber @ MgAl hydrotalcite composite film prepared in examples 1 to 7 to Pb (II).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
The embodiment provides a carbon fiber @ MgAl hydrotalcite composite film combining carbon fibers and magnesium aluminum hydrotalcite, and the preparation method comprises the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and drying the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1. urea:
in a molar ratio of (A), MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of water and ethanol (ethanol volume is 60%), and making into MgSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 0.896g of MgSO was weighed out4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621g urea in 50mL of mixed solvent of water and ethanol (the volume of the ethanol is 60%), stirring uniformly, transferring into a 100mL reaction kettle with a polytetrafluoroethylene lining, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
SEM photographs of the carbon paper and the carbon fiber @ MgAl hydrotalcite composite film are shown as a and b in fig. 1, respectively. As can be seen from a and b in fig. 1, the carbon fiber surface of the carbon paper is smooth, while the hydrotalcite-loaded carbon fiber surface presents continuous and dense hydrotalcite sheets, and part of the flaky hydrotalcite is agglomerated into spheres, so that the carbon fiber surface becomes rough.
The XRD pattern of each film is shown in FIG. 2. B in fig. 2 shows that the characteristic peak of magnesium-aluminum hydrotalcite appears at 2 θ ═ 11.5 in the carbon fiber @ MgAl hydrotalcite composite film, indicating that the hydrotalcite is successfully grown on the carbon fiber.
The carbon paper and the carbon fiber @ MgAl hydrotalcite composite film prepared in the embodiment are used for adsorbing 50mL of 20mg/L Pb (II) solution, the pH value of the Pb (II) solution is adjusted to 6.0 by using 0.1mol/L NaOH solution, and the untreated carbon paper has no adsorption effect on Pb (II); in contrast, when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in this example reaches the equilibrium, the residual concentration of Pb (II) in the solution is measured to be 1.7mg/L, the adsorption rate of Pb (II) is measured to be 96.5%, and the adsorption amount is measured to be 10.5 mg/g.
Example 2
In this embodiment, on the basis of example 1, the proportion of ethanol in the mixed solvent is reduced, the amount of the metal salt is reduced by half, the hydrothermal reaction temperature is increased, the hydrothermal reaction time is prolonged, and the carbon fiber @ MgAl hydrotalcite composite film is optimized. The preparation method of the carbon fiber @ MgAl hydrotalcite composite film comprises the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and then performing common drying on the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
the MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of water and ethanol (ethanol volume is 30%), and making into MgSO4The concentration is 0.036mol/L, Al2(SO4)3The concentration of the precursor solution is 0.012 mol/L.
Specifically, 0.448g of MgSO was weighed out4·7H2O、0.202g Al2(SO4)3·18H2Dissolving O and 1.311g of urea in 50mL of mixed solvent of water and ethanol (the volume of the ethanol is 30%), stirring uniformly, transferring into a 100mL reaction kettle with a polytetrafluoroethylene lining, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 18h at 130 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ MgAl hydrotalcite composite thin film of the present example is shown as c in fig. 1. As can be seen from c in fig. 1, under the preparation conditions of this example, the hydrotalcite growth amount on the carbon fiber surface is substantially unchanged, the hydrotalcite sheets are uniformly distributed, and the agglomeration phenomenon is reduced as compared with example 1.
The XRD spectrum of the carbon fiber @ MgAl hydrotalcite composite film of the embodiment is shown in figure 2. B in fig. 2 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of magnesium aluminum hydrotalcite at 2 θ ═ 11.5, indicating that hydrotalcite is successfully grown on carbon fiber.
The carbon fiber @ MgAl hydrotalcite composite film prepared in the example adsorbs 50mL of 20mg/L Pb (II) solution, the pH value of the carbon fiber @ MgAl hydrotalcite composite film is adjusted to 6.0 by using 0.1mol/L NaOH solution, and when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in the example reaches the balance, the residual concentration of Pb (II) in the solution is measured to be 5.1mg/L, the adsorption rate of Pb (II) is measured to be 74.5%, and the adsorption capacity is measured to be 8.6 mg/g.
Example 3
The embodiment further reduces the proportion of ethanol in the mixed solvent, reduces the dosage of metal salt, reduces the hydrothermal reaction temperature, prolongs the hydrothermal reaction time, and optimizes the carbon fiber and hydrotalcite composite film. The preparation method of the carbon fiber @ MgAl hydrotalcite composite film comprises the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and drying the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
the MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of water and ethanol (ethanol volume is 10%), and making into MgSO4The concentration is 0.0036mol/L, Al2(SO4)3The concentration is 0.0012 mol/L.
Specifically, 0.045g of MgSO was weighed4·7H2O、0.02g Al2(SO4)3·18H2O and 0.131g of urea, and mixing the obtained mixtureDissolving the mixture in 50mL of mixed solvent of water and ethanol (the volume of the ethanol is 10 percent), stirring the mixture evenly, transferring the mixture into a 100mL reaction kettle with a polytetrafluoroethylene lining, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 24 hours at 90 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ MgAl hydrotalcite composite thin film of the present example is shown as d in fig. 1. As can be seen from d in fig. 1, under the preparation conditions of this example, the hydrotalcite growth amount on the carbon fiber surface is substantially unchanged, the hydrotalcite sheets are uniformly distributed, and the agglomeration phenomenon is reduced as compared with example 1.
The XRD spectrum of the carbon fiber @ MgAl hydrotalcite composite film prepared in the embodiment is shown in figure 2. B in fig. 2 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of magnesium aluminum hydrotalcite at 2 θ ═ 11.5, indicating that hydrotalcite is successfully grown on carbon fiber.
The carbon fiber @ MgAl hydrotalcite composite film prepared in the example adsorbs 50mL of 20mg/L Pb (II) solution, the pH value of the Pb (II) solution is adjusted to 6.0 by using 0.1mol/L NaOH solution, and when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in the example reaches the equilibrium, the adsorption rate of Pb (II) residual concentration of 12.5mg/L, Pb (II) in the solution is 37.5%, and the adsorption capacity is 4.3 mg/g.
Example 4
In this embodiment, the time and temperature of the hydrothermal reaction are increased on the basis of embodiment 1, and the carbon fiber @ MgAl hydrotalcite composite film is optimized. The preparation method of the carbon fiber @ MgAl hydrotalcite composite film comprises the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and then performing common drying on the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
the MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in 50mL of mixed solvent of water and ethanol (ethanol volume is 60%) to obtain MgSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 0.896g of MgSO was weighed out4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621g urea in 50mL of mixed solvent of water and ethanol (the volume of the ethanol is 60%), stirring uniformly, transferring into a 100mL reaction kettle with a polytetrafluoroethylene lining, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 10h at 150 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ MgAl hydrotalcite composite film obtained in this example is shown as e in fig. 1. As can be seen from e in fig. 1, under the preparation conditions of this example, the hydrotalcite growth amount on the carbon fiber surface is substantially unchanged, the hydrotalcite sheets are uniformly distributed, and the agglomeration phenomenon of the hydrotalcite sheets is avoided.
The XRD spectrum of the carbon fiber @ MgAl hydrotalcite composite film prepared in the embodiment is shown in figure 2. B in fig. 2 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of magnesium aluminum hydrotalcite at 2 θ ═ 11.5, indicating that hydrotalcite is successfully grown on carbon fiber.
When the carbon fiber @ MgAl hydrotalcite composite film prepared in the example adsorbs 50mL of 20mg/L Pb (II) solution and the pH value is adjusted to 6.0 by using 0.1mol/L NaOH solution, the adsorption rate of Pb (II) residual concentration of 5.1mg/L, Pb (II) in the solution is 74.5% and the adsorption amount is 8.6mg/g when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in the example reaches the equilibrium.
Example 5
In this embodiment, on the basis of example 1, ethanol is replaced by methanol, and a one-step solvothermal carbon fiber @ MgAl hydrotalcite composite film is adopted, where the preparation method includes the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and then performing common drying on the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
the MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of water and methanol (methanol volume is 60%) to obtain MgSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 0.896g of MgSO was weighed out4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621g urea in 50mL of mixed solvent of water and methanol (the volume of the methanol is 60%), stirring uniformly, transferring into a 100mL reaction kettle with a polytetrafluoroethylene lining, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ MgAl hydrotalcite composite film prepared in this example is shown as f in fig. 1. As can be seen from f in fig. 1, under the preparation conditions of this example, the hydrotalcite growth amount on the carbon fiber surface is substantially unchanged, the distribution of hydrotalcite sheets is uniform, the agglomeration phenomenon is reduced compared with that of example 1, and the hydrotalcite sheets are reduced.
The XRD spectrum of the carbon fiber @ MgAl hydrotalcite composite film prepared in the example is shown in figure 2. B in fig. 2 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of magnesium aluminum hydrotalcite at 2 θ ═ 11.5, indicating that hydrotalcite is successfully grown on carbon fiber.
The carbon fiber @ MgAl hydrotalcite composite film prepared in the example adsorbs 50mL of 20mg/L Pb (II) solution, the pH value of the solution is adjusted to 6.0 by using 0.1mol/L NaOH solution, when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in the example reaches the balance, the residual concentration of Pb (II) in the solution is measured to be 0.04mg/L, the adsorption rate of Pb (II) is measured to be 99.8%, and the adsorption capacity is measured to be 11.5 mg/g.
Example 6
In this embodiment, on the basis of example 1, ethanol is replaced by n-propanol, and a one-step solvothermal method is used to prepare a carbon fiber @ MgAl hydrotalcite composite film, where the preparation method includes the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and then performing common drying on the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
the MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea with a mixture of water and n-propanol (n-propanol volume is 60%) to obtain MgSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 0.896g of MgSO was weighed out4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621g of urea in 50mL of mixed solvent of water and n-propanol (the volume of the n-propanol is 60%), stirring uniformly, transferring into a 100mL reaction kettle lined with polytetrafluoroethylene, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. Reaction ofAnd after the completion of the cooling, cooling to room temperature, washing the carbon paper with deionized water until no white solid is on the surface of the carbon paper, and then drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ MgAl hydrotalcite composite film obtained in this example is shown in g in fig. 1. It can be seen from g in fig. 1 that, under the preparation conditions of this example, the hydrotalcite growth amount on the carbon fiber surface is substantially unchanged, the hydrotalcite sheets are uniformly distributed, and the agglomeration phenomenon is reduced as compared with example 1.
The XRD spectrum of the carbon fiber @ MgAl hydrotalcite composite film prepared in the example is shown in figure 2. B in fig. 2 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of magnesium aluminum hydrotalcite at 2 θ ═ 11.5, indicating that hydrotalcite is successfully grown on carbon fiber.
The carbon fiber @ MgAl hydrotalcite composite film prepared in the example adsorbs 50mL of 20mg/L Pb (II) solution, the pH value of the carbon fiber @ MgAl hydrotalcite composite film is adjusted to 6.0 by using 0.1mol/L NaOH solution, when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in the example reaches the balance, the residual concentration of Pb (II) in the solution is measured to be 2.4mg/L, the adsorption rate of Pb (II) is 91%, and the adsorption quantity is 10.1 mg/g.
Example 7
In this embodiment, on the basis of example 1, ethanol is replaced by isopropanol, and a one-step solvothermal carbon fiber @ MgAl hydrotalcite composite film is adopted, where the preparation method includes the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and then performing common drying on the carbon paper at 80 ℃ for 12h for later use.
(2) According to MgSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
the MgSO is weighed4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of water and isopropanol (60% by volume of isopropanol) to obtain MgSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 0.896g of MgSO was weighed out4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621g of urea in 50mL of mixed solvent of water and isopropanol (60% by volume of isopropanol), stirring uniformly, transferring into a 100mL reaction kettle lined with polytetrafluoroethylene, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ MgAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ MgAl hydrotalcite composite film prepared in this example is shown as h in fig. 1. As can be seen from h in fig. 1, under the preparation conditions of this example, the hydrotalcite growth amount on the carbon fiber surface is substantially unchanged, the hydrotalcite sheets are uniformly distributed, and the agglomeration phenomenon is reduced as compared with example 1.
The XRD spectrum of the carbon fiber @ MgAl hydrotalcite composite film prepared in the example is shown in figure 2. B in fig. 2 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of magnesium aluminum hydrotalcite at 2 θ ═ 11.5, indicating that hydrotalcite is successfully grown on carbon fiber.
The carbon fiber @ MgAl hydrotalcite composite film prepared in the example adsorbs 50mL of 20mg/L Pb (II) solution, the pH value of the solution is adjusted to 6.0 by using 0.1mol/L NaOH solution, when the adsorption of the carbon fiber @ MgAl hydrotalcite prepared in the example reaches the balance, the residual concentration of Pb (II) in the solution is measured to be 3.1mg/L, the adsorption rate of Pb (II) is 84.5%, and the adsorption capacity is 9.7 mg/g.
Example 8
In this embodiment, on the basis of example 1, a magnesium salt is replaced with a nickel salt, and a one-step solvothermal carbon fiber @ NiAl hydrotalcite composite film is provided, where the preparation method includes the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment on the carbon paper in 20mL of acetone, ethanol and water for 10min (the ultrasonic power is 180W), and then performing common drying on the carbon paper at 80 ℃ for 12h for later use.
(2) According to NiSO4·6H2O：Al2(SO4)3·18H2O is 3: 1, urea:
weighing NiSO according to the molar ratio4·6H2O、Al2(SO4)3·18H2Dissolving O and urea in mixed solution of water and ethanol (ethanol volume is 60%), and making into NiSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 0.961g of NiSO was weighed4·6H2O、0.404g Al2(SO4)3·18H2Dissolving O and 5.242 urea in 50mL of mixed solvent of water and ethanol (ethanol accounts for 60 percent by volume), stirring uniformly, transferring into a 100mL reaction kettle lined with polytetrafluoroethylene, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and then drying at 80 ℃ for 12 hours to obtain the carbon fiber @ NiAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ NiAl hydrotalcite composite film obtained in this example is shown as i in fig. 1. In fig. 1, i shows that a large number of uniform NiAl hydrotalcite sheets are grown on the surface of the carbon fiber in the carbon fiber @ NiAl hydrotalcite composite film prepared in this example, but the sheets are small, about 200nm, which indicates that the NiAl hydrotalcite can be grown on the carbon fiber under the solvothermal condition.
The XRD spectrum of the carbon fiber @ NiAl hydrotalcite composite film prepared in the example is shown in figure 3. B in fig. 3 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of NiAl hydrotalcite at 2 θ ═ 11.5, indicating that the NiAl hydrotalcite is successfully grown on carbon fibers.
Example 9
In this embodiment, on the basis of example 1, a magnesium salt is replaced with a cobalt salt, and a one-step solvothermal method is adopted to prepare a carbon fiber @ CoAl hydrotalcite composite film, where the preparation method includes the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment in 20mL of acetone, ethanol and water for 10min (ultrasonic power is 180W), and drying the carbon paper at 80 ℃ for 12h for later use.
(2) According to CoSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
weighing CoSO in the molar ratio4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in a mixed solution of water and ethanol (ethanol volume is 60%) to obtain CoSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 1.017g of CoSO were weighed4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621 urea in 50mL of mixed solvent of water and ethanol (ethanol accounts for 60 percent by volume), stirring uniformly, transferring into a 100mL reaction kettle lined with polytetrafluoroethylene, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ CoAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ CoAl hydrotalcite composite film obtained in this example is shown as j in fig. 1. J in fig. 1 shows that only relatively dense flaky CoAl hydrotalcite particles are grown on the surface of the carbon fiber in the carbon fiber @ CoAl hydrotalcite composite film prepared in this example, but the flaky particles are not uniform in size.
The XRD pattern of the carbon fiber @ CoAl hydrotalcite composite film prepared in the example is shown in figure 3. B in fig. 3 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of the CoAl hydrotalcite at 2 θ ═ 11.5, indicating that the hydrotalcite was successfully grown on carbon fibers.
Example 10
In this embodiment, on the basis of example 1, a magnesium salt is replaced with a zinc salt, and a one-step solvothermal method is adopted to prepare a carbon fiber @ ZnAl hydrotalcite composite film, where the preparation method includes the following steps:
(1) cutting the carbon paper into a rectangle with the size of 3.5 x 3cm, sequentially performing ultrasonic treatment in 20mL of acetone, ethanol and water for 10min (ultrasonic power is 180W), and drying the carbon paper at 80 ℃ for 12h for later use.
(2) According to ZnSO4·7H2O：Al2(SO4)3·18H2O is 3: 1, urea:
weighing ZnSO according to the molar ratio4·7H2O、Al2(SO4)3·18H2Dissolving O and urea in mixed solution of water and ethanol (ethanol volume is 60%), and making into ZnSO4The concentration is 0.072mol/L, Al2(SO4)3Precursor solution with the concentration of 0.024 mol/L.
Specifically, 1.04g of ZnSO was weighed4·7H2O、0.404g Al2(SO4)3·18H2Dissolving O and 2.621 urea in 50mL of mixed solvent of water and ethanol (ethanol accounts for 60 percent by volume), stirring uniformly, transferring into a 100mL reaction kettle lined with polytetrafluoroethylene, and adding the carbon paper prepared in the step (1). And sealing the reaction kettle, and carrying out hydrothermal reaction for 12h at 110 ℃ to enable the hydrotalcite to grow on the carbon paper in situ. And after the reaction is finished, cooling to room temperature, washing the carbon paper with deionized water until no white solid exists on the surface of the carbon paper, and drying at 80 ℃ for 12 hours to obtain the carbon fiber @ ZnAl hydrotalcite composite film.
An SEM photograph of the carbon fiber @ ZnAl hydrotalcite composite film obtained in this example is shown as k in fig. 1. In fig. 1, k shows that only dense and uniform lamellar ZnAl hydrotalcite is grown on the surface of the carbon fiber in the carbon fiber @ ZnAl hydrotalcite composite film prepared in this example, which indicates that ZnAl hydrotalcite can be grown on the carbon fiber under solvothermal conditions.
The XRD pattern of the carbon fiber @ ZnAl hydrotalcite composite film prepared in the embodiment is shown in figure 3. B in fig. 3 shows that the XRD pattern of the sample prepared in this example shows characteristic peaks of ZnAl hydrotalcite at 2 θ ═ 13, indicating that ZnAl hydrotalcite is successfully grown on carbon fibers.
Example 11
The embodiment provides a preparation method of an adsorbent for removing heavy metal ions in an aqueous solution, in particular for removing Pb (II), which comprises the steps of adjusting the pH of the aqueous solution containing the heavy metal Pb (II) to 6.0 by using 0.1mol/L NaOH solution, and adding a carbon fiber @ MgAl hydrotalcite composite film to adsorb the Pb (II), so that the heavy metal ions Pb (II) can be removed.
For example, 0.1mol/L NaOH solution is added to 50mL of 20mg/L Pb (II) solution, the pH is adjusted to 6.0, 0.087g of the carbon fiber @ MgAl hydrotalcite composite film of any one of examples 1 to 7 is added, and Pb (II) is adsorbed on the carbon fiber @ MgAl hydrotalcite composite film under the oscillation condition of 150r/min at 25 ℃.
For comparison, carbon papers of the same mass were separately added to the Pb (II) solution to adsorb Pb (II) under the same conditions. The adsorption results of Pb (II) by the respective films are shown in Table 1 and FIG. 4.
Table 1 shows the comparison of the adsorption data of the carbon fiber @ MgAl hydrotalcite composite films prepared in examples 1 to 7 on Pb (II)
Note: carbon paper @ MgAl hydrotalcite was prepared on the basis of example 1, using only water as solvent.
As can be seen from Table 1 and FIG. 4, the MgAl hydrotalcite and the carbon fiber are combined by the one-step solvothermal method, so that the composite material has a certain adsorption effect on Pb (II); the amount of alcohol added had a large influence on the adsorption effect, and the adsorption amount of Pb (II) was 10.5mg/L and the adsorption rate was 96.5% under the production conditions of example 1, and the adsorption amount of Pb (II) was 11.5mg/L and the adsorption rate was 99.8% and was about 100% under the production conditions of example 5.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon fiber @ MAL hydrotalcite composite film is characterized by comprising the following steps:
(1) cleaning and drying the carbon paper for later use;
(2) weighing divalent metal salt and Al2(SO4)3·18H2Dissolving O and urea in mixed solution of alcohol and water, wherein divalent metal salt is magnesium salt, nickel salt, cobalt salt or zinc salt, urea and water
The ratio of the amounts of substances of (a) to (b) is 8: 1, the ratio of the amount of the divalent metal ions to the amount of the trivalent metal ions is 2-4: 1; uniformly stirring the obtained solution, transferring the solution into a hydrothermal reaction kettle, and putting the carbon paper treated in the step (1) into the solution;
and (2) sealing the hydrothermal reaction kettle, then carrying out hydrothermal reaction, naturally cooling to room temperature after the reaction is completed, washing the carbon paper with water until no white solid is on the surface of the carbon paper, and then drying to obtain the carbon fiber @ MAL hydrotalcite composite film, wherein M is Mg, Ni, Co or Zn.
2. The preparation method of the carbon fiber @ MAl hydrotalcite composite film according to claim 1, wherein in the step (1), the carbon paper is sequentially subjected to ultrasonic treatment in acetone, ethanol and water, and then dried.
3. The preparation method of the carbon fiber @ MAl hydrotalcite composite film according to claim 1, wherein the amount of the divalent metal salt substance in the step (2): the volume of the mixed solution of alcohol and water was 0.00018 to 0.0036mol/50 mL.
4. The preparation method of the carbon fiber @ MAl hydrotalcite composite film according to claim 1, wherein the alcohol in the step (2) comprises any one of methanol, ethanol, n-propanol and isopropanol; the volume ratio of the alcohol in the mixed solution of the alcohol and the water in the step (2) is 10-60%.
5. The method for preparing the carbon fiber @ MAl hydrotalcite composite film according to claim 1, wherein the divalent metal salt in the step (2) comprises one of magnesium sulfate, magnesium chloride, magnesium nitrate, zinc sulfate, zinc chloride, zinc nitrate, cobalt sulfate, cobalt chloride, cobalt nitrate, nickel sulfate, nickel chloride and nickel nitrate.
6. The preparation method of the carbon fiber @ MAl hydrotalcite composite film according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 90-150 ℃, and the time of the hydrothermal reaction is 10-24 h.
7. The preparation method of the carbon fiber @ MAL hydrotalcite composite film according to claim 1, wherein the carbon fiber @ MAL hydrotalcite composite film is a carbon fiber @ MgAl hydrotalcite composite film, and the preparation steps are as follows:
(1) cleaning and drying the carbon paper for later use;
(2) weighing magnesium salt and Al2(SO4)3·18H2O and urea, and dissolving in a mixed solution of methanol and water, wherein the urea and the water
The ratio of the amounts of substances of (a) to (b) is 8: 1, divalent metal ion and trivalent metal ion Al3+The ratio of the amounts of substances of (a) to (b) is 3: 1, the volume ratio of methanol in the mixed solution of methanol and water is 60 percent; uniformly stirring the obtained solution, transferring the solution into a hydrothermal reaction kettle, and putting the carbon paper treated in the step (1) into the solution; and sealing the hydrothermal reaction kettle, carrying out hydrothermal reaction at 110 ℃ for 12h, naturally cooling to room temperature after the reaction is completed, washing the carbon paper with water until no white solid is on the surface of the carbon paper, and drying to obtain the carbon fiber @ MgAl hydrotalcite composite film.
8. A carbon fiber @ MAl hydrotalcite composite film made by the process of any of claims 1-7 wherein M ═ Mg, Ni, Co, or Zn.
9. Use of the carbon fiber @ MAl hydrotalcite composite film according to claim 8 for adsorbing heavy metal ions in an aqueous solution.
10. Use according to claim 9, characterized in that the heavy metal ion is Pb (ii).
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