CN111974359A - Preparation and application of nano-cellulose/layered double-metal hydroxide composite material with adsorptivity and in-situ catalysis performance - Google Patents
Preparation and application of nano-cellulose/layered double-metal hydroxide composite material with adsorptivity and in-situ catalysis performance Download PDFInfo
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Abstract
The invention relates to nanocellulose/laminal with adsorption and in-situ catalysisPreparation and application of a double-metal hydroxide composite material, belonging to the field of preparation of bio-based materials. The preparation method comprises the following steps: sequentially adding CuSO to the nanocellulose suspension4NaOH is subjected to in-situ precipitation to obtain CuO/nano-cellulose; and carrying out solution intercalation on the matrix MgAl layered hydroxide by using the CuO/nano-cellulose as a modifier and a reinforcing agent to obtain the nano-cellulose/layered double-metal hydroxide composite material. Adding the composite material into 50mL of 20 mg/L4-nitrophenol solution, adding 30mg of NaBH4, and measuring the residual concentration of 4-nitrophenol in the solution and the concentration of generated 4-aminophenol by adopting an ultraviolet spectrophotometry. The preparation method provided by the invention is simple, convenient to operate, strong in practicability, easy to recover and strong in environmental protection, and can solve the problem of water pollution in the current society.
Description
Technical Field
The invention belongs to the field of preparation of biological base materials, and particularly relates to a preparation method of a nano-cellulose/MgAl layered double-metal hydroxide composite material.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the increasingly prominent environmental protection problem, the development of high-efficiency, low-consumption and environmentally-friendly wastewater treatment technologies and materials becomes a new research hotspot. Among a plurality of treatment technologies, the adsorption method is the preferred method for treating wastewater pollutants due to the advantages of low treatment cost, high efficiency, simple operation and the like. However, the single adsorption technology has the problem of the maximum saturated adsorption capacity of the adsorbent, and the unreasonable regeneration or disposal after the adsorption is finished is easy to cause secondary pollution, so that the coupling of the adsorption method and the in-situ catalysis method for treating the wastewater becomes a new direction for research.
Due to the two-dimensional layered structure of the layered double hydroxide, various adjustable denaturation and unique physicochemical properties endowed by various metal elements, the application of the layered double hydroxide in the aspects of adsorption and catalysis is widely concerned. The nano-cellulose is a renewable polymer material with high strength and high mechanical property, and has rich sources. A large number of active hydroxyl groups exist on the surface of the nano-cellulose, which is beneficial to the mutual permeation and modification with a polymer matrix. How to prepare the degradable modified bio-based material by utilizing the characteristics of the nano-cellulose, widening the application performance and improving the market value of the material is a problem to be solved at present.
Disclosure of Invention
The invention provides a preparation method of a nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis. CuO/nano-cellulose is used as a modifier and a reinforcing agent, and a novel composite adsorption catalytic material is prepared by carrying out solution intercalation on MgAl layered hydroxide of a matrix, so that the composite adsorption catalytic material has adsorbability and in-situ catalytic performance, can be used for treating dye wastewater and can be recycled.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a method for preparing a nanocellulose/layered double hydroxide composite material with adsorptivity and in-situ catalysis is provided, which comprises the following steps:
sequentially adding CuSO to the nanocellulose suspension4NaOH is subjected to in-situ precipitation to obtain CuO/nano-cellulose;
and carrying out solution intercalation on the matrix MgAl layered hydroxide by using the CuO/nano-cellulose as a modifier and a reinforcing agent to obtain the nano-cellulose/layered double-metal hydroxide composite material.
The research of the invention finds that: the MgAl layered double hydroxide is modified by using CuO/nano-cellulose as a modifier and a reinforcing agent, so that the MgAl layered double hydroxide has the capacity of adsorbing and reducing 4-nitrophenol in wastewater in situ.
In a second aspect of the invention, there is provided a nanocellulose/layered double hydroxide composite material with adsorption and in-situ catalysis prepared by any one of the above methods.
The composite material has the capacity of adsorbing and catalyzing 4-nitrophenol in situ, can be recovered by centrifugal washing, and is a clean product.
In a third aspect of the invention, the application of the nano-cellulose/layered double hydroxide composite material with adsorptivity and in-situ catalysis in wastewater treatment is provided. Wherein the wastewater contains 4-nitrophenol.
According to the invention, the CuO/modified nano-cellulose modified layered double hydroxide is used for treating the wastewater containing 4-nitrophenol, so that the use of chemicals is reduced, and the treatment efficiency is improved.
The invention has the beneficial effects that:
(1) the invention takes the nano-cellulose and the layered double hydroxide as raw materials, and has the advantages of environmental protection and reproducibility.
(2) The composite material has the capacity of adsorbing and catalyzing 4-nitrophenol in situ, can be recovered by centrifugal washing, and is a clean product.
(3) The preparation method is simple, strong in adsorption and catalysis capacity, strong in practicability and good in economic and environmental benefits.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Background art along with more and more attach importance to environmental problems, especially under the present condition that water resource is very deficient, handle sewage and be the must way of solving the quality of water problem. Therefore, the invention provides a preparation method of a nano-cellulose/layered double hydroxide composite material with adsorbability and in-situ catalysis, which takes CuO/nano-cellulose as a modifier and a reinforcing agent and MgAl layered hydroxide as a matrix to carry out solution intercalation to prepare a novel composite adsorption catalysis material, so that the composite adsorption catalysis material has adsorbability and in-situ catalysis performance, can be used for treating dye wastewater and can be recycled.
One of the purposes of the invention is to provide a preparation method of a novel adsorption catalytic material.
The second purpose of the invention is to utilize CuO/nano-cellulose as a modifier to intercalate and compound MgAl layered double hydroxides so as to achieve the purposes of adsorbing and catalyzing 4-nitrophenol in situ.
The nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis property is characterized in that CuO/nano-cellulose is used as a modifier and a reinforcing agent to modify MgAl layered double-metal hydroxide, so that the MgAl layered double-metal hydroxide composite material has the capacity of adsorbing and in-situ reducing 4-nitrophenol in wastewater;
in some embodiments, the modification method comprises the following specific steps: dispersing CuO/nano-cellulose in a matrix water suspension, and reacting for 5-6 h at 50-60 ℃. After the CuO/nano-cellulose and MgAl layered hydroxide are subjected to solution intercalation compounding, the adsorption performance and catalytic degradation performance of the composite material are improved.
The specific specification of the nanocellulose is not particularly limited, and therefore, in some embodiments, the nanocellulose has a length of 500-2000 nm and a diameter of 10-50nm, so as to obtain better adsorption performance and mechanical performance.
The preparation method of CuO/nanocellulose is not particularly limited, and thus, in some embodiments, CuO/nanocellulose is prepared from CuSO4And NaOH are precipitated in situ in the nano-cellulose suspension for preparation; to obtain better loading efficiency and catalytic performance.
In some embodiments, the loading of CuO in the nanocellulose is from 10 to 20 wt%; effectively improves the adsorption performance and the catalytic degradation performance of the composite material.
In some embodiments, the ratio of the amount of CuO/nanocellulose to MgAl layered double hydroxide is 2: 1-1: 4; the absorption and in-situ catalytic performance of the composite material are ensured, and the utilization rate of the raw materials is improved.
In some embodiments, the solid-to-liquid ratio of the nanocellulose/layered double hydroxide composite to the 4-nitrophenol-containing wastewater is 5-20 mg: 50mL, so as to effectively remove the 4-nitrophenol in the wastewater and improve the removal rate.
In some embodiments, the composite material is recovered by centrifugation for the purpose of green, environmental friendly, renewable recycling.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
A preparation method of a nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis comprises the following specific steps:
1) preparation of CuO/nano-cellulose: a) preparing 1.0 wt% nanocellulose aqueous suspension and stirring, adding CuSO4Heating a water bath to 75 ℃, slowly adding 1mol/L NaOH into the nano-cellulose suspension, and stirring for reaction for 4 hours. b) After the reaction is finished, centrifugal washing is carried out until the pH value is neutral, and the lower-layer precipitate is CuO/nano-cellulose, wherein the CuO loading amount is 10 wt%.
2) Nanocellulose/layered double hydroxide composite: a) preparing 2.0 wt% of MgAl layered double hydroxide aqueous suspension, mixing and stirring for 1h, and adding CuO/nano cellulose in the step 1), wherein the dosage ratio of CuO/nano cellulose to MgAl layered double hydroxide is 2: 1. b) setting the temperature of the water bath kettle to 50 ℃, stirring for reaction for 5 hours, then centrifugally washing, and obtaining the lower-layer precipitate which is the nano-cellulose/layered double-metal hydroxide composite material.
3) Adsorption and in-situ catalytic degradation of the composite material on 4-nitrophenol: adding 5mg of the composite material into 50mL of 20 mg/L4-nitrophenol solution, and adding 30mg of NaBH4Placing in a water bath constant temperature oscillator (120rpm), centrifuging after 20min, collecting supernatant, and measuring residual concentration of 4-nitrophenol and concentration of generated 4-aminophenol in the solution by ultraviolet spectrophotometry.
Example 2
A preparation method of a nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis comprises the following specific steps:
1) of CuO/nanocellulosePreparation: a) preparing 1.0 wt% nanocellulose aqueous suspension and stirring, adding CuSO4Heating a water bath to 75 ℃, slowly adding 1mol/L NaOH into the nano-cellulose suspension, and stirring for reaction for 4 hours. b) After the reaction is finished, centrifugal washing is carried out until the pH value is neutral, and the lower-layer precipitate is CuO/nano-cellulose, wherein the CuO loading is 15 wt%.
2) Nanocellulose/layered double hydroxide composite: a) preparing 2.0 wt% of MgAl layered double hydroxide aqueous suspension, mixing and stirring for 1h, and adding CuO/nano cellulose in the step 1), wherein the dosage ratio of CuO/nano cellulose to MgAl layered double hydroxide is 1: 1. b) setting the temperature of the water bath kettle to 50 ℃, stirring for reaction for 5 hours, then centrifugally washing, and obtaining the lower-layer precipitate which is the nano-cellulose/layered double-metal hydroxide composite material.
3) Adsorption and in-situ catalytic degradation of the composite material on 4-nitrophenol: adding 10mg of the composite material into 50mL of 20 mg/L4-nitrophenol solution, and adding 30mg of NaBH4Placing in a water bath constant temperature oscillator (120rpm), centrifuging after 20min, collecting supernatant, and measuring residual concentration of 4-nitrophenol and concentration of generated 4-aminophenol in the solution by ultraviolet spectrophotometry.
Example 3
A preparation method of a nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis comprises the following specific steps:
1) preparation of CuO/nano-cellulose: a) preparing 1.0 wt% nanocellulose aqueous suspension and stirring, adding CuSO4Heating a water bath to 75 ℃, slowly adding 1mol/L NaOH into the nano-cellulose suspension, and stirring for reaction for 4 hours. b) After the reaction is finished, centrifugal washing is carried out until the pH value is neutral, and the lower-layer precipitate is CuO/nano-cellulose, wherein the CuO loading amount is 20 wt%.
2) Nanocellulose/layered double hydroxide composite: a) preparing 2.0 wt% of MgAl layered double hydroxide aqueous suspension, mixing and stirring for 1h, and adding CuO/nano cellulose in the step 1), wherein the dosage ratio of CuO/nano cellulose to MgAl layered double hydroxide is 1: 1. b) setting the temperature of the water bath kettle to 50 ℃, stirring for reaction for 5 hours, then centrifugally washing, and obtaining the lower-layer precipitate which is the nano-cellulose/layered double-metal hydroxide composite material.
3) Adsorption and in-situ catalytic degradation of the composite material on 4-nitrophenol: adding 10mg of the composite material into 50mL of 20 mg/L4-nitrophenol solution, adding 30mg of NaBH4, placing in a water bath constant temperature oscillator (120rpm), centrifuging after 20min, collecting supernatant, and measuring the residual concentration of 4-nitrophenol in the solution and the concentration of generated 4-aminophenol by adopting an ultraviolet spectrophotometry.
Example 4
A preparation method of a nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis comprises the following specific steps:
1) preparation of CuO/nano-cellulose: a) preparing 1.0 wt% nanocellulose aqueous suspension and stirring, adding CuSO4Heating a water bath to 75 ℃, slowly adding 1mol/L NaOH into the nano-cellulose suspension, and stirring for reaction for 4 hours. b) After the reaction is finished, centrifugal washing is carried out until the pH value is neutral, and the lower-layer precipitate is CuO/nano-cellulose, wherein the CuO loading is 15 wt%.
2) Nanocellulose/layered double hydroxide composite: a) preparing 2.0 wt% of MgAl layered double hydroxide aqueous suspension, mixing and stirring for 1h, and adding CuO/nano cellulose in the step 1), wherein the dosage ratio of CuO/nano cellulose to MgAl layered double hydroxide is 1: 1. b) setting the temperature of the water bath kettle to 50 ℃, stirring for reaction for 5 hours, then centrifugally washing, and obtaining the lower-layer precipitate which is the nano-cellulose/layered double-metal hydroxide composite material.
3) Adsorption and in-situ catalytic degradation of the composite material on 4-nitrophenol: adding 20mg of the composite material into 50mL of 20 mg/L4-nitrophenol solution, adding 30mg of NaBH4, placing in a water bath constant temperature oscillator (120rpm), centrifuging after 20min, collecting supernatant, and measuring the residual concentration of 4-nitrophenol in the solution and the concentration of generated 4-aminophenol by adopting an ultraviolet spectrophotometry.
Example 5
A preparation method of a nano-cellulose/layered double-metal hydroxide composite material with adsorbability and in-situ catalysis comprises the following specific steps:
1) preparation of CuO/nano-cellulose: a) preparing 1.0 wt% nanocellulose aqueous suspension and stirring, adding CuSO4Heating a water bath to 75 ℃, slowly adding 1mol/L NaOH into the nano-cellulose suspension, and stirring for reaction for 4 hours. b) After the reaction is finished, centrifugal washing is carried out until the pH value is neutral, and the lower-layer precipitate is CuO/nano-cellulose, wherein the CuO loading is 15 wt%.
2) Nanocellulose/layered double hydroxide composite: a) preparing 2.0 wt% of MgAl layered double hydroxide aqueous suspension, mixing and stirring for 1h, and adding CuO/nano cellulose in the step 1), wherein the dosage ratio of CuO/nano cellulose to MgAl layered double hydroxide is 1: 4. b) setting the temperature of the water bath kettle to 50 ℃, stirring for reaction for 5 hours, then centrifugally washing, and obtaining the lower-layer precipitate which is the nano-cellulose/layered double-metal hydroxide composite material.
3) Adsorption and in-situ catalytic degradation of the composite material on 4-nitrophenol: adding 20mg of the composite material into 50mL of 20 mg/L4-nitrophenol solution, adding 30mg of NaBH4, placing in a water bath constant temperature oscillator (120rpm), centrifuging after 20min, collecting supernatant, and measuring the residual concentration of 4-nitrophenol in the solution and the concentration of generated 4-aminophenol by adopting an ultraviolet spectrophotometry.
Comparative example 1
The difference from example 1 is that "nanocellulose" was used instead of "CuO/nanocellulose".
Comparative example 2
The difference from example 1 is that "CuO/nanocellulose" was not added.
And (3) performance testing:
the concentration of 4-nitrophenol remaining in the supernatant after the composite material prepared in examples 1-5 had been treated with 4-nitrophenol was determined using the concentration of 4-nitrophenol in the solution as an index for performance testing. The test method comprises the following steps: 0.005g/L, 0.001g/L, 0.0015g/L, 0.002g/L and 0.0025g/L of 4-nitrophenol standard samples are respectively prepared, placed in an ultraviolet visible spectrophotometer to measure absorbance, and a standard curve is determined, as shown in Table 1. The filtrates were separately placed in an ultraviolet-visible spectrophotometer to measure absorbance, and the concentrations thereof were calculated from the standard curves, with the test results shown in table 2.
TABLE 14 UV-VISIBLE Absorbance of Nitrophenol and 4-aminophenol standards
| Concentration of 4-nitrophenol/g/L | 0.0005 | 0.001 | 0.0015 | 0.002 | 0.0025 |
| absorbance/T% | 0.02286 | 0.03559 | 0.04033 | 0.04875 | 0.05715 |
| 4-aminophenol concentration/g/L | 0.0005 | 0.001 | 0.0015 | 0.002 | 0.0025 |
| absorbance/T% | 0.01982 | 0.03046 | 0.03987 | 0.04678 | 0.05515 |
According to calculation, the standard curve is Y1 ═ 16.827X1+0.0151
The standard curve is Y2 ═ 17.396X2+0.0123
Wherein X1 is the concentration of 4-nitrophenol, g/L; y1 is the UV/Vis absorbance, T%.
X2 is 4-aminophenol concentration, g/L; y2 is the UV/Vis absorbance, T%.
TABLE 2 concentrations of 4-nitrophenol and 4-aminophenol in the supernatant after treatment of 4-nitrophenol with the composites prepared in examples 1-5
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Absorbance/T1% | 0.0451 | 0.0231 | 0.0261 | 0.0193 | 0.0424 | 0.0518 | 0.1839 |
| concentration/mg/L | 1.784 | 0.476 | 0.652 | 0.250 | 1.622 | 2.1815 | 10.0291 |
| Removal rate/%) | 91.08 | 97.62 | 96.74 | 98.75 | 91.89 | 89.0927 | 49.8545 |
| Absorbance/T2% | 0.2919 | 0.3211 | 0.3136 | 0.3265 | 0.3009 | — | — |
| concentration/mg/L | 16.07 | 17.75 | 17.32 | 18.06 | 16.59 | — | — |
| Conversion rate/% | 80.36 | 88.74 | 86.62 | 90.31 | 82.95 | — | — |
As can be seen from Table 2, the nanocellulose/layered double hydroxide composite material prepared by the method can be used for efficiently catalyzing and degrading 4-nitrophenol in a short time.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a nano-cellulose/layered double hydroxide composite material with adsorbability and in-situ catalysis is characterized by comprising the following steps:
sequentially adding CuSO to the nanocellulose suspension4NaOH is subjected to in-situ precipitation to obtain CuO/nano-cellulose;
and carrying out solution intercalation on the matrix MgAl layered hydroxide by using the CuO/nano-cellulose as a modifier and a reinforcing agent to obtain the nano-cellulose/layered double-metal hydroxide composite material.
2. The method for preparing the nano-cellulose/layered double hydroxide composite material with adsorbability and in-situ catalysis property according to claim 1, wherein the ratio of the dosage of the CuO/nano-cellulose to the dosage of the MgAl layered double hydroxide is 1-2: 1 to 4.
3. The method for preparing a nanocellulose/layered double hydroxide composite material with adsorption and in-situ catalysis properties according to claim 1, wherein the loading of CuO in the CuO/nanocellulose is 10-20 wt%.
4. The preparation method of the nano-cellulose/layered double hydroxide composite material with adsorptivity and in-situ catalysis property as claimed in claim 1, wherein the specific condition of the in-situ precipitation is that the reaction is carried out for 4-6 h at 75-85 ℃.
5. The method for preparing the nano-cellulose/layered double hydroxide composite material with adsorptivity and in-situ catalysis property as claimed in claim 1, wherein the nano-cellulose has a length of 500-2000 nm and a diameter of 10-50 nm.
6. The method for preparing the nano-cellulose/layered double hydroxide composite material with adsorptivity and in-situ catalysis according to claim 1, wherein the solution intercalation comprises the following specific steps: dispersing CuO/nano-cellulose in matrix MgAl layered hydroxide aqueous suspension, and reacting for 5-6 h at 50-60 ℃.
7. The method for preparing nano-cellulose/layered double hydroxide composite material with adsorptivity and in-situ catalysis property according to claim 6, wherein the mass concentration of the MgAl layered hydroxide aqueous suspension is 1.0 wt% to 5.0 wt%.
8. The nanocellulose/layered double hydroxide composite having adsorptive and in-situ catalytic properties prepared by the method of any one of claims 1-7.
9. Use of the adsorptive and in situ catalytic nanocellulose/layered double hydroxide composite of claim 8 for wastewater treatment.
10. The use according to claim 9, wherein the wastewater contains 4-nitrophenol.
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