CN113000031A - Zinc oxide/collagen fiber composite porous adsorption material and preparation method and application thereof - Google Patents
Zinc oxide/collagen fiber composite porous adsorption material and preparation method and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 102000008186 Collagen Human genes 0.000 title claims abstract description 151
- 108010035532 Collagen Proteins 0.000 title claims abstract description 151
- 229920001436 collagen Polymers 0.000 title claims abstract description 151
- 239000000835 fiber Substances 0.000 title claims abstract description 149
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 96
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229960000314 zinc acetate Drugs 0.000 claims abstract description 56
- 239000004246 zinc acetate Substances 0.000 claims abstract description 56
- 239000000725 suspension Substances 0.000 claims abstract description 25
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 238000004043 dyeing Methods 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 239000012876 carrier material Substances 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 30
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 15
- 238000000151 deposition Methods 0.000 description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 14
- 229940043267 rhodamine b Drugs 0.000 description 14
- 230000008569 process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 241001388119 Anisotremus surinamensis Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 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
- B01J20/22—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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a zinc oxide/collagen fiber composite porous adsorption material and a preparation method and application thereof, belonging to the field of adsorbent preparation. Taking collagen fibers as a carrier material, firstly introducing anhydrous zinc acetate on the collagen fibers by adopting low-temperature circulating impregnation treatment, and then placing the collagen fibers in a mixed solution of the zinc acetate and sodium hydroxide for water bath deposition to obtain a zinc oxide/collagen fiber composite suspension; freezing the obtained zinc oxide/collagen fiber composite suspensionAnd drying to obtain the zinc oxide/collagen fiber composite porous adsorption material. The zinc oxide/collagen fiber composite porous adsorption material prepared by the preparation method can be used as a printing and dyeing wastewater agent for Pb in printing and dyeing wastewater2+，Cr6+，Hg2+，Cu2+，Fe3+Adsorption of heavy metal ions and degradation of dyes.
Description
Technical Field
The invention belongs to the field of adsorbent preparation, and relates to a zinc oxide/collagen fiber composite porous adsorption material, and a preparation method and application thereof.
Background
With the acceleration of the industrialization process, the random discharge of industrial wastewater causes serious environmental problems, and the treatment problem of printing and dyeing wastewater in the textile industry is particularly prominent. The printing and dyeing wastewater contains a large amount of pollutants such as organic dyes and heavy metal ions, has the characteristics of high toxicity, carcinogenicity, biological accumulation and the like, and more scholars try to find a simple and effective treatment method. The commonly used treatment methods include chemical precipitation, ion exchange, membrane separation, ultrafiltration, photocatalytic degradation and adsorption. The adsorption method is an industrial wastewater treatment method with wide application due to the advantages of simple operation, high efficiency, easy scale production and the like, and a proper adsorption material is one of the keys of the adsorption method. In recent years, researchers often make the adsorbing material into a nanometer form or compound the adsorbing material with other functional nanometer materials, so that the specific surface area, the surface energy and the chemical reaction activity of the adsorbing material are improved, and finally the adsorption capacity and the adsorption rate of the adsorbing material are improved.
Zinc oxide (ZnO) as an important inorganic nano material has the characteristics of large specific surface area, more surface active centers, no toxicity and the like, can effectively absorb ultraviolet light and generate a large amount of photoinduced electrons and holes, so that the zinc oxide has excellent adsorption and degradation properties in the aspect of printing and dyeing wastewater treatment. But also has the defects that self agglomeration is easy to occur due to higher surface energy in the preparation and application processes, so that the specific surface area is reduced, and the powder material is inconvenient to separate after being adsorbed. Therefore, how to avoid the agglomeration of ZnO is the key point for improving the adsorption degradation performance of ZnO. At present, special micro-nano structures are mainly constructed or compounded with materials with high specific surface area to improve the dispersion degree of the micro-nano structures and inhibit groupsAnd polymerization is carried out, so that the adsorption degradation performance is improved. For example, Caoming et al (CN106268642A) used a hydrothermal method, with sodium tartrate as a morphology inducer and urea or hexamethylenetetramine as a precipitant, to obtain a composite adsorbent with high specific surface area and high uniform dispersion of pompon zinc oxide particles on graphene surface, and used for the treatment of Cr6+The maximum adsorption capacity of (a) is 360 mg/g. However, in the method, graphene oxide is used as a carrier material, so that the preparation cost is increased, and high-temperature reaction is adopted, so that great requirements on equipment and an operating environment are met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a zinc oxide/collagen fiber composite porous adsorption material, a preparation method and application thereof, and solves the problem that zinc oxide is easy to agglomerate and is difficult to separate.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a zinc oxide/collagen fiber composite porous adsorption material, which comprises the steps of taking collagen fibers as a carrier material, introducing anhydrous zinc acetate on the collagen fibers by adopting low-temperature circulating impregnation treatment, and then placing the collagen fibers in a mixed solution of the zinc acetate and sodium hydroxide for water bath deposition to obtain a zinc oxide/collagen fiber composite suspension; and (3) carrying out freeze drying treatment on the obtained zinc oxide/collagen fiber composite suspension to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Preferably, the specific operations of the low-temperature cyclic dipping treatment include: soaking collagen fibers in a zinc acetate solution, and then drying to obtain a primary soaking treatment operation; and circulating the impregnation treatment operation to introduce anhydrous zinc acetate.
Further preferably, the cycle number of the dipping treatment operation is 3 to 6.
Further preferably, the soaking temperature is 15-55 ℃, the soaking time is 1-10 min, and the drying temperature is 20-60 ℃.
Further preferably, the mass ratio of the collagen fibers to the zinc acetate in the zinc acetate solution is 1: (0.2-0.6).
Further preferably, the concentration of the zinc acetate solution is 0.01-0.05 moL/L.
Preferably, in the mixed solution of zinc acetate and sodium hydroxide, the mass ratio of zinc acetate to sodium hydroxide is 1: (4-8).
Preferably, the treatment temperature of the water bath deposition is 20-60 ℃, and the treatment time is 3-7 h.
The invention discloses a zinc oxide/collagen fiber composite porous adsorption material prepared by the preparation method.
The invention discloses an application of the zinc oxide/collagen fiber composite porous adsorption material in printing and dyeing wastewater treatment.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a zinc oxide/collagen fiber composite porous adsorption material, which adopts a simple low-temperature circulating impregnation treatment method to interweave, coat and wind collagen fibers on the surface of zinc oxide, thereby not only solving the defect that a powdered zinc oxide material is easy to agglomerate and difficult to separate, facilitating the recovery and the reutilization of an adsorbent, but also reserving rich oxygen-containing functional groups on the collagen fibers and providing more adsorption sites, and the zinc oxide can also play a role in enhancing the mechanical strength of the collagen fibers. Anhydrous zinc acetate in the collagen fibers is initiated to nucleate through low-temperature hydrolysis in a zinc acetate and sodium hydroxide aqueous solution, and the obtained zinc oxide grows in situ between the collagen fibers, so that the mechanical strength of the collagen fibers is improved; through freeze drying treatment, the original three-dimensional porous structure of the collagen fiber can be maintained, and more active adsorption sites are provided. Therefore, the preparation method disclosed by the invention is simple in preparation process, low in energy consumption, green and environment-friendly in preparation process and suitable for large-scale industrial application.
Further, in the low-temperature circulating dipping treatment process, zinc acetate is subjected to dehydration reaction through low-temperature drying treatment, so that the anhydrous zinc acetate and collagen fiber composite material is obtained.
Further, in the mixed solution of zinc acetate and sodium hydroxide, the pH value of the solution is too high, so that the zinc acetate generates a complex Zn (OH)4 2-。
Further, OH in the mixed solution of zinc acetate and sodium hydroxide is utilized-So that the anhydrous zinc acetate is forcedly hydrolyzed in situ between the collagen fibers to generate the nano ZnO nucleus.
Further, with the complex Zn (OH)4 2-Increased concentration of (a), in addition to OH-High chemical potential, so that the complex Zn (OH)4 2-The nano ZnO nucleus formed by the anhydrous zinc acetate promotes the heterogeneous nucleation growth of the ZnO crystal on the collagen fiber.
Furthermore, the low-temperature water bath deposition and freeze drying treatment are adopted, so that the original oxygen-containing functional groups in the collagen fibers can be maintained, the three-dimensional porous structure of the collagen fibers can not be damaged, and more active sites are provided for adsorbing pollutants.
The invention discloses a zinc oxide/collagen fiber composite porous adsorption material prepared by the preparation method, which has a large specific surface area and abundant active sites and can effectively adsorb pollutants in wastewater.
The invention also discloses application of the zinc oxide/collagen fiber composite porous adsorption material as a dye degradation catalyst. The zinc oxide/collagen fiber composite porous adsorption material provided by the invention utilizes oxygen-containing functional groups such as hydroxyl and the like contained in zinc oxide and collagen fiber, and can be combined with heavy metal ions in printing and dyeing wastewater through electrostatic adsorption to adsorb the heavy metal ions.
Furthermore, by utilizing the photocatalytic degradation characteristic of zinc oxide, in the photocatalytic reaction process, the collagen fiber material has the functions of enrichment and storage, and compared with the direct reaction under the aqueous solution environment, the collagen fiber material can store a large amount of dye molecules under the uniformly dispersed environment, so that the reaction efficiency is greatly improved, the degradation of the adsorbed dye can be realized under visible light, and the desorption cost is reduced.
Therefore, the invention realizes the preparation of the zinc oxide/collagen fiber composite porous adsorption material under the low temperature condition, has simple preparation process, low energy consumption and green and environment-friendly preparation process, is suitable for large-scale industrial application, and has important significance for the treatment of printing and dyeing wastewater.
Drawings
FIG. 1 is SEM photographs of the zinc oxide/collagen fiber composite porous adsorbing material prepared in example 3 of the invention under different magnifications;
FIG. 2 shows the Pb pair of the zinc oxide/collagen fiber composite porous adsorption material prepared in example 3 of the invention2+，Cr6+，Hg2+Graph of adsorption isotherms of (a);
FIG. 3 shows the preparation of the zinc oxide/collagen fiber composite porous adsorbent material for Cu according to example 3 of the present invention2+，Fe3+Graph of adsorption isotherms of (a);
fig. 4 is a photocatalytic degradation curve of rhodamine B when the zinc oxide/collagen fiber composite porous adsorption material prepared in example 3 of the present invention is used as a visible light catalyst.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
A preparation method of a zinc oxide/collagen fiber composite porous adsorption material comprises the following steps:
firstly, soaking collagen fibers in a zinc acetate solution at the soaking temperature of 15-55 ℃ for 1-10 min, drying in an oven at the temperature of 20-60 ℃ after soaking is finished, completing a soaking treatment step, and repeating the soaking treatment step for 3-6 times, namely introducing anhydrous zinc acetate on the collagen fibers based on a low-temperature circulating soaking treatment method to obtain the treated collagen fibers; then, soaking the treated collagen fiber into a mixed solution of zinc acetate and sodium hydroxide, and performing water bath deposition to obtain a zinc oxide/collagen fiber composite suspension; and (3) carrying out freeze drying treatment on the obtained zinc oxide/collagen fiber composite suspension to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Wherein, the volume ratio of the zinc acetate solution to the mixed solution of zinc acetate and sodium hydroxide is 1: 1.
specifically, the dosage of the zinc acetate solution is 2-10 mL, and the concentration is 0.01-0.05 moL/L.
Specifically, the mass ratio of the collagen fibers to the zinc acetate in the zinc acetate solution is 1: (0.2-0.6).
Specifically, the using amount of the mixed solution of zinc acetate and sodium hydroxide is 2-10 mL, and the mass ratio of the zinc acetate to the sodium hydroxide is 1: (4-8).
Specifically, the treatment temperature of the water bath deposition is 20-60 ℃, and the treatment time is 3-7 h.
Specifically, in the embodiment of the invention, the obtained zinc oxide/collagen fiber composite porous adsorption material has the function of adsorbing Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent respectively reach 130-520 mg/g, 80-380 mg/g, 130-350 mg/g, 10-27 mg/g and 12-28 mg/g; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min can reach 85-96 percent under visible light.
The invention is described in further detail below with reference to the following figures and specific examples:
example 1:
soaking 0.05g of collagen fiber into 4mL of 0.02moL/L zinc acetate solution, soaking at 15 ℃ for 10min, drying in an oven at 40 ℃ after soaking is finished, repeating the steps for 4 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 4mL of a mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:5), and depositing in a water bath at 60 ℃ for 5 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are 457mg/g, 340mg/g, 275mg/g, 17mg/g and 18.6mg/g respectively; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min reaches 88 percent under visible light.
Example 2:
soaking 0.1g of collagen fiber into 3mL of 0.05moL/L of zinc acetate solution, soaking at 15 ℃ for 5min, drying in an oven at 40 ℃ after soaking is finished, repeating the steps for 3 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 3mL of mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:6), and depositing in a water bath at 30 ℃ for 5 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+In a constant temperature of 30 deg.CAdsorbing in a shaking table for 12 h. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are 455mg/g, 330mg/g, 270mg/g, 16.5mg/g and 18mg/g respectively; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min can reach 87 percent under visible light.
Example 3:
soaking 0.05g of collagen fiber into 3mL of 0.05moL/L of zinc acetate solution, soaking at 55 ℃ for 1min, drying in an oven at 40 ℃ after soaking is finished, repeating the steps for 5 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 3mL of mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:8), and performing water bath deposition at 20 ℃ for 7 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are respectively 520mg/g, 380mg/g, 350mg/g, 27mg/g and 28 mg/g; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min can reach 96 percent under visible light.
As shown in fig. 1, the zinc oxide obtained by the low-temperature circulating impregnation method is mainly in a rod-shaped structure, the diameter of the zinc oxide is about 200-300 nm, and collagen fibers are interlaced, coated and wound on the surface of the rod-shaped zinc oxide to form a porous structure; FIG. 2 shows the Pb pair of the zinc oxide/collagen fiber composite porous adsorbing material in example 32+，Cr6+，Hg2+Adsorption isotherm plot of (a); FIG. 3 shows the zinc oxide/collagen fiber composite porous adsorption material for Cu in example 32+，Fe3+Graph of adsorption isotherms of (a); FIG. 4 shows the zinc oxide/collagen fiber composite porous adsorption of example 3The material is used as a photocatalytic degradation curve of a visible light catalyst for rhodamine B (RhB), and the photocatalytic degradation rate of the material in 60min for rhodamine B with the concentration of 10mg/L under visible light reaches 96%.
Example 4:
soaking 0.15g of collagen fiber into 6mL of 0.03moL/L zinc acetate solution, soaking at 40 ℃ for 5min, drying in an oven at 50 ℃ after soaking, repeating the steps for 4 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 6mL of a mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:7), and depositing in a water bath at 40 ℃ for 6 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are respectively 450mg/g, 326mg/g, 261mg/g, 15mg/g and 16 mg/g; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min can reach 85 percent under visible light.
Example 5:
soaking 0.2g of collagen fiber into 10mL of 0.04moL/L zinc acetate solution, soaking for 8min at 20 ℃, drying in an oven at 30 ℃ after soaking, repeating the steps for 6 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 10mL of mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:4), and depositing in a water bath at 50 ℃ for 3 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Mixing the above 0.1g of oxygenThe zinc oxide/collagen fiber composite porous adsorption materials are respectively dispersed in the Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are 468mg/g, 358mg/g, 280mg/g, 19mg/g and 20mg/g respectively; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min can reach 89% under visible light.
Example 6:
soaking 0.1g of collagen fiber in 5mL of 0.05moL/L zinc acetate solution at 25 ℃ for 7min, drying in an oven at 55 ℃ after soaking, repeating the steps for 6 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 5mL of a mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:5), and depositing in a water bath at 30 ℃ for 4 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are 498mg/g, 370mg/g, 295mg/g, 20mg/g and 22mg/g respectively; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min reaches 91 percent under visible light.
Example 7:
soaking 0.11g of collagen fiber into 8mL of 0.04moL/L zinc acetate solution, soaking at 30 ℃ for 6min, drying in an oven at 35 ℃ after soaking is finished, repeating the steps for 5 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 8mL of mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:8), and depositing in a water bath at 30 ℃ for 4 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are respectively 501mg/g, 374mg/g, 130mg/g, 22.4mg/g and 23 mg/g; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min reaches 93 percent under visible light.
Example 8:
soaking 0.09g of collagen fiber in 2mL of 0.05moL/L zinc acetate solution at 50 ℃ for 2min, drying in an oven at 60 ℃ after soaking, repeating the steps for 5 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 2mL of a mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:6), and depositing in a water bath at 45 ℃ for 5.5 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are 445mg/g, 80mg/g, 268mg/g, 10mg/g and 12mg/g respectively; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min can reach 92 percent under visible light.
Example 9:
soaking 0.04g of collagen fiber into 9mL of 0.01moL/L zinc acetate solution, soaking at 30 ℃ for 6min, drying in an oven at 60 ℃ after soaking, repeating the steps for 5 times, and introducing anhydrous zinc acetate into the collagen fiber to obtain the treated collagen fiber; soaking the treated collagen fibers in 9mL of mixed solution of zinc acetate and sodium hydroxide (the mass ratio of the zinc acetate to the sodium hydroxide is 1:4), and depositing in a water bath at 35 ℃ for 4 hours to obtain a zinc oxide/collagen fiber composite suspension; and (3) freeze-drying the obtained zinc oxide/collagen fiber composite suspension for 12 hours at the temperature of-20 ℃ and under the pressure of 0.1Pa to obtain the zinc oxide/collagen fiber composite porous adsorption material.
Respectively dispersing the 0.1g zinc oxide/collagen fiber composite porous adsorption material in Pb-containing materials2+，Cr6+，Hg2+The solution was adsorbed for 12 hours in a constant temperature shaker at a temperature of 30 ℃. After reaching adsorption equilibrium, the material is aligned to Pb2+，Cr6+，Hg2+，Cu2+，Fe3+The adsorption capacities of the adsorbent are respectively 130mg/g, 368mg/g, 293mg/g, 19.5mg/g and 21.6 mg/g; the photocatalytic degradation rate of rhodamine B with the concentration of 10mg/L in 60min reaches 90 percent under visible light.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a zinc oxide/collagen fiber composite porous adsorption material is characterized in that collagen fibers are used as a carrier material, firstly, low-temperature circulating dipping treatment is adopted to introduce anhydrous zinc acetate on the collagen fibers, and then the collagen fibers are placed in a mixed solution of the zinc acetate and sodium hydroxide for water bath deposition to obtain a zinc oxide/collagen fiber composite suspension; and (3) carrying out freeze drying treatment on the obtained zinc oxide/collagen fiber composite suspension to obtain the zinc oxide/collagen fiber composite porous adsorption material.
2. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material according to claim 1, wherein the specific operation of the low-temperature cycle impregnation treatment comprises: soaking collagen fibers in a zinc acetate solution, and then drying to obtain a primary soaking treatment operation; and circulating the impregnation treatment operation to introduce anhydrous zinc acetate.
3. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material according to claim 2, wherein the cycle number of the dipping treatment operation is 3-6.
4. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material according to claim 2, wherein the soaking temperature is 15-55 ℃, the soaking time is 1-10 min, and the drying temperature is 20-60 ℃.
5. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material according to claim 2, wherein the mass ratio of the collagen fibers to the zinc acetate in the zinc acetate solution is 1: (0.2-0.6).
6. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material as claimed in claim 2, wherein the concentration of the zinc acetate solution is 0.01-0.05 moL/L.
7. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material according to claim 1, wherein the mass ratio of zinc acetate to sodium hydroxide in the mixed solution of zinc acetate and sodium hydroxide is 1: (4-8).
8. The preparation method of the zinc oxide/collagen fiber composite porous adsorption material according to claim 1, wherein the treatment temperature of the water bath deposition is 20-60 ℃ and the treatment time is 3-7 h.
9. The zinc oxide/collagen fiber composite porous adsorption material prepared by the preparation method of any one of claims 1 to 8.
10. The use of a zinc oxide/collagen fiber composite porous adsorbent material as claimed in claim 9 in the treatment of printing and dyeing wastewater.
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