CN114392770B - Preparation method of cellulose-based photocatalytic material with weak photocatalytic performance - Google Patents
Preparation method of cellulose-based photocatalytic material with weak photocatalytic performance Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 100
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 28
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 41
- 238000000967 suction filtration Methods 0.000 claims description 37
- 239000012153 distilled water Substances 0.000 claims description 19
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 19
- 229960002218 sodium chlorite Drugs 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
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- 238000005054 agglomeration Methods 0.000 abstract description 3
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- 238000011084 recovery Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 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 21
- 229940043267 rhodamine b Drugs 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 21
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- 241000588724 Escherichia coli Species 0.000 description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006142 Luria-Bertani Agar Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
A preparation method of a cellulose-based photocatalytic material with weak photocatalytic performance relates to a preparation method of a photocatalytic material. The invention aims to solve the problems of easy falling, agglomeration, difficult recovery, low light utilization rate and poor weak light catalytic performance of the traditional powder suspension phase photocatalysis system. The method comprises the following steps: 1. preparing a cellulose aqueous solution; 2. adding the photocatalytic material into the cellulose water solution, performing ultrasonic treatment, and finally performing freeze drying to obtain the cellulose-based photocatalytic material with weak photocatalytic performance. The photocatalysis material prepared by the invention can realize weak photocatalysis due to a special microstructure, can be normally used when being applied to places with weak indoor equal light intensity, and can realize optimal catalysis effect in the shortest time. The invention can obtain a cellulose-based photocatalytic material with weak photocatalytic performance.
Description
Technical Field
The invention relates to a preparation method of a photocatalytic material.
Background
Among photocatalytic systems, powder suspension systems are the most common and convenient systems. Powder suspension systems have inherent disadvantages:
1. easy to fall off: it is difficult to load on an object, so the utilization rate is low. The Gibbs free energy on the surface of the nano-scale photocatalyst is high, the nano-scale photocatalyst is easy to agglomerate, and even if the nano-scale photocatalyst starts to disperse, the nano-scale photocatalyst can be slowly aggregated together along with the use of materials, and the utilization rate is low.
2. Agglomeration: the nanometer particles are easy to attract each other, so that the specific surface area of the catalyst is reduced, the effective contact area with pollutants is reduced, and electron-hole pairs generated by illumination are easy to recombine and deactivate. Eventually leading to an affected photocatalytic reaction efficiency.
3. Recovery is difficult: the nano particles are difficult to settle and separate under the action of gravity, so that a centrifuge is necessary to separate, thus increasing the complexity and cost of wastewater treatment and causing secondary pollution. The particles are easy to lose activity after being soaked in the wastewater for a long time.
4. The traditional powder needs to be further molded by a binder, so that adsorption sites are easily diluted, even pore channels collapse and are blocked, and further the adsorption capacity and selectivity are reduced.
5. Light utilization problem: the light efficiency and the utilization rate of the traditional powder system are generally low, for example, some suspended matters and deeper chromaticity in certain waste water (such as printing and dyeing waste water) are not beneficial to light transmission, and the photocatalysis effect is influenced. More importantly, with the popularization of indoor photocatalytic products, the potential market for weak photocatalytic products is extremely large, but weak photocatalytic products with high-efficiency catalytic performance are extremely few on the market.
Disclosure of Invention
The invention aims to solve the problems of easy falling, agglomeration, difficult recovery, low light utilization rate and poor weak light catalytic performance of the existing powder suspension phase photocatalytic system, and provides a preparation method of a cellulose-based photocatalytic material with weak light catalytic performance.
The preparation method of the cellulose-based photocatalytic material with weak photocatalytic performance is specifically completed by the following steps:
1. preparation of an aqueous cellulose solution:
(1) extracting the wood powder by using a Soxhlet extraction method by taking a mixed solution of acetic acid and sodium chlorite as a solvent;
(2) repeating the step one (1), carrying out suction filtration, and finally cleaning the solid matters obtained by suction filtration to be neutral by using distilled water to obtain solid matters A;
(3) putting the cellulose A into NaOH solution, heating, filtering, and washing the solid matters obtained by filtering with distilled water to obtain solid matters B;
(4) firstly, immersing a solid substance B into a mixed solution of acetic acid and sodium chlorite, then heating, carrying out suction filtration, immersing the solid substance obtained by suction filtration into a NaOH solution, heating, carrying out suction filtration, and finally washing the solid substance obtained by suction filtration to be neutral by using distilled water to obtain cellulose;
(5) adding cellulose into deionized water, and then treating by using an ultrasonic pulverizer to obtain a cellulose aqueous solution;
2. adding the photocatalytic material into the cellulose water solution, performing ultrasonic treatment, and finally performing freeze drying to obtain the cellulose-based photocatalytic material with weak photocatalytic performance.
The invention has the advantages that:
1. effective catalyst/dye loading:
the cellulose is wrapped with the anchored catalyst by curling, so that a large number of nano particles are uniformly and stably anchored in the cellulose structure, and the loading capacity of the catalyst or dye is increased;
2. high specific surface area due to porous structure:
the dye has enough active sites, prevents inactivation, has unique pore structure and empty size as a carrier, can control the reactive position and the localized structure, has high selectivity to the reaction, and can adsorb more single-layer dye molecules;
3. absorption efficiency of light:
the invention has micro-nano porous structure, sunlight can be reflected for many times in the rough surface of the cellulose-based photocatalytic material prepared by the invention so as to be repeatedly absorbed by pollutants (materials to be degraded), the light receiving area is increased, the light absorption efficiency is increased, and the utilization rate of the sunlight is greatly improved;
4. high-efficiency pre-adsorption:
pre-adsorption is a precondition for efficient photodecomposition, and sample porous structure pre-adsorption is one of the greatest advantages; the pollutant is contacted with the surface of the catalyst through adsorption and filtration, so that the aim of high-efficiency treatment is fulfilled; the synergy of (coupling adsorption and photocatalysis) adsorption and photocatalysis can improve the kinetic constant by more than 2 times; the (combined physical adsorption and high-performance adsorption carrier) topological structure can be used as an adsorbent, so that pollutants can be enriched near a photocatalyst, photogenerated electrons can be received, the recombination with holes is inhibited, and more reaction interfaces are provided;
5. the preparation process is environment-friendly, good in durability and easy to operate in subsequent application.
6. The photocatalysis material prepared by the invention can realize weak photocatalysis due to a special microstructure, can be normally used when being applied to places with weak indoor equal light intensity, and can realize optimal catalysis effect in the shortest time;
7. the preparation cost is low, the photocatalytic material and cellulose can be molded in one step, and other materials such as graphene oxide and the like are not needed to be added, so that the cost is further saved.
Drawings
FIG. 1 is a macroscopic digital photograph of a cellulose-based photocatalytic material having weak photocatalytic properties prepared in example one;
FIG. 2 is an SEM image of pure cellulose prepared by a conventional process;
FIG. 3 is an SEM image of a cellulose-based photocatalytic material having weak photocatalytic properties prepared according to example I;
fig. 4 is a graph showing the adsorption capacity test of a sample, wherein 1 is the absorbance of rhodamine B solution, 2 is the absorbance after dark adsorption of rhodamine B solution for 3 hours by using pure cellulose prepared by the conventional process, and 3 is the absorbance after dark adsorption of rhodamine B solution for 3 hours by using the cellulose-based photocatalytic material with weak photocatalytic performance prepared in example one;
FIG. 5 is a graph of photocatalytic efficiency, wherein 1 is pure cellulose and 2 is TiO 2 3 is absorbance of the ultraviolet light region of the cellulose-based photocatalytic material with weak photocatalytic performance prepared in the first embodiment for adsorbing rhodamine B;
FIG. 6 shows the absorbance of pure cellulose prepared by the conventional process at different times under 20 lux light intensity irradiation to adsorb rhodamine B solution;
FIG. 7 shows the absorbance of a cellulose-based photocatalytic material having weak photocatalytic properties prepared in example I under irradiation with a light intensity of 20 lux, which adsorbs rhodamine B solution at different times;
FIG. 8 is a toxicity test chart.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
The first embodiment is as follows: the preparation method of the cellulose-based photocatalytic material with weak photocatalytic performance in the embodiment is specifically completed by the following steps:
1. preparation of an aqueous cellulose solution:
(1) extracting the wood powder by using a Soxhlet extraction method by taking a mixed solution of acetic acid and sodium chlorite as a solvent;
(2) repeating the step one (1), carrying out suction filtration, and finally cleaning the solid matters obtained by suction filtration to be neutral by using distilled water to obtain solid matters A;
(3) putting the cellulose A into NaOH solution, heating, filtering, and washing the solid matters obtained by filtering with distilled water to obtain solid matters B;
(4) firstly, immersing a solid substance B into a mixed solution of acetic acid and sodium chlorite, then heating, carrying out suction filtration, immersing the solid substance obtained by suction filtration into a NaOH solution, heating, carrying out suction filtration, and finally washing the solid substance obtained by suction filtration to be neutral by using distilled water to obtain cellulose;
(5) adding cellulose into deionized water, and then treating by using an ultrasonic pulverizer to obtain a cellulose aqueous solution;
2. adding the photocatalytic material into the cellulose water solution, performing ultrasonic treatment, and finally performing freeze drying to obtain the cellulose-based photocatalytic material with weak photocatalytic performance.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the extraction temperature in the step one (1) is 80-85 ℃, and the extraction time is 1-2 h; and (3) repeating the step one (1)3 to 5 times) in the step one (2). The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: and (3) putting the cellulose A into NaOH solution, heating to 75-80 ℃, treating for 1-2 h at 75-80 ℃, carrying out suction filtration, and washing the solid matters obtained by suction filtration by using distilled water to obtain solid matters B. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: in the first step (4), firstly, immersing the solid substance B into a mixed solution of acetic acid and sodium chlorite, then heating to 80-85 ℃, treating for 1-2 h at 80-85 ℃, then carrying out suction filtration, immersing the solid substance obtained by suction filtration into a NaOH solution, treating for 1-2 h at 80-85 ℃, finally carrying out suction filtration, and washing the solid substance obtained by suction filtration to be neutral by using distilled water to obtain cellulose. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the mixed solution of the acetic acid and the sodium chlorite in the step one (1) and the step one (4) is that the acetic acid and the sodium chlorite are dissolved in distilled water, wherein the concentration of the acetic acid is 1.3 mol/L-1.5 mol/L, and the concentration of the sodium chlorite is 0.12 mol/L-0.15 mol/L; the concentration of the NaOH solution in the step one (3) and the step one (4) is 0.30mol/L to 0.35mol/L. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the mass fraction of the cellulose aqueous solution in the step one (5) is 0.1-0.2%. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the power of the ultrasonic pulverizer in the step one (5) is 800W, and the treatment time is 30-40 min. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the power of the ultrasound in the second step is 650W-700W, and the ultrasound time is 5 min-10 min; the temperature of the freeze drying in the second step is-40 ℃ to-50 ℃, and the time of the freeze drying is 20h to 30h. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the photocatalytic material in the second step is titanium dioxide, zinc dioxide or tin oxide; the particle size of the photocatalytic material in the second step is 100 nm-1000 nm. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the mass fraction of the photocatalytic material in the cellulose-based photocatalytic material with weak photocatalytic performance in the second step is 25% -30%. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one: the preparation method of the cellulose-based photocatalytic material with weak photocatalytic performance is specifically completed by the following steps:
1. preparation of an aqueous cellulose solution:
(1) extracting the wood powder by using a Soxhlet extraction method by taking a mixed solution of acetic acid and sodium chlorite as a solvent, wherein the extraction temperature is 80 ℃, and the extraction time is 1h;
(2) repeating the first step (1)4 times, carrying out suction filtration again, and finally washing the solid matters obtained by suction filtration to be neutral by using distilled water to obtain solid matters A;
(3) placing cellulose A into NaOH solution, heating to 80 ℃, treating for 2 hours at 80 ℃, carrying out suction filtration, and finally washing a solid substance obtained by suction filtration by using distilled water to obtain a solid substance B;
(4) immersing a solid substance B into a mixed solution of acetic acid and sodium chlorite, heating to 85 ℃, treating for 1.5 hours at 85 ℃, carrying out suction filtration, immersing the solid substance obtained by suction filtration into a NaOH solution, heating to 85 ℃, treating for 1.5 hours at 85 ℃, carrying out suction filtration, and finally washing the solid substance obtained by suction filtration to be neutral by using distilled water to obtain cellulose;
the mixed solution of the acetic acid and the sodium chlorite in the step one (1) and the step one (4) is prepared by dissolving the acetic acid and the sodium chlorite into distilled water, wherein the concentration of the acetic acid is 1.3mol/L, and the concentration of the sodium chlorite is 0.12mol/L;
the concentration of the NaOH solution in the step one (3) and the step one (4) is 0.35mol/L;
(5) adding cellulose into deionized water, and then treating for 40min by using an ultrasonic pulverizer with the power of 800W to obtain a cellulose aqueous solution;
the mass fraction of the cellulose aqueous solution in the step one (5) is 0.1%;
2. adding titanium dioxide with the particle size of 300nm into a cellulose water solution, performing ultrasonic treatment for 5min under the ultrasonic power of 700W, and finally performing freeze drying for 20h at the temperature of 50 ℃ below zero to obtain a cellulose-based photocatalytic material with weak photocatalytic performance;
the mass fraction of titanium dioxide in the cellulose-based photocatalytic material with weak photocatalytic performance in the second step is 30%.
Comparative examples: the pure cellulose prepared by the conventional process is cellulose powder, and 50 μm (CAS: 9004-34-6) is purchased from Shanghai A Ding Gongsi.
FIG. 1 is a macroscopic digital photograph of a cellulose-based photocatalytic material having weak photocatalytic properties prepared in example one;
from the macroscopic picture of fig. 1, it can be clearly observed that the sample has an ultra-high weight ratio and an ultra-low density.
FIG. 2 is an SEM image of pure cellulose prepared by a conventional process;
as can be seen from fig. 2, the pure cellulose is in the form of irregular sheets or coarse filaments.
FIG. 3 is an SEM image of a cellulose-based photocatalytic material having weak photocatalytic properties prepared according to example I;
as can be seen from fig. 3, the titanium dioxide is uniformly distributed on the cellulose filaments and is uniformly anchored by the cellulose filaments, which provides a method for creating a unique nanoscale chemical environment, which is separated from the surrounding bulk space to generate a micro-nano limiting phenomenon, and effectively solves the problem that the powdery catalyst is easy to agglomerate.
The samples were compressed under the same external conditions and the results were visible. The specific surface area of the cellulose-based photocatalytic material with weak photocatalytic performance obtained by the method in the first embodiment is about 5 times higher than that of pure cellulose prepared by the traditional process, and the cellulose-based photocatalytic material with weak photocatalytic performance obtained by the method in the first embodiment has micropores and mesopores at the same time, so that the simultaneous existence of the micropores and the mesopores is the key for obtaining high capacity. Meanwhile, the high specific surface area can possess enough active sites to inhibit deactivation. The cellulose-based photocatalytic material with weak photocatalytic performance obtained by the method of example one has a unique pore structure and void size as a carrier, and can control the reactive sites and localized structures, as shown in table 1.
TABLE 1
Adsorption performance test:
50mg of the cellulose-based photocatalytic material having weak photocatalytic properties prepared in example one was addedIs added into 30mL and has the concentration of 4000 mg.L －1 Performing dark adsorption for 3 hours in rhodamine B solution, and measuring the absorbance of the solution by using an ultraviolet spectrophotometer, wherein the absorbance is shown as a curve 3 in fig. 4;
50mg of pure cellulose prepared by the conventional process (the pure cellulose prepared by the conventional process is cellulose powder, 50 μm (CAS: 9004-34-6) purchased from Shanghai A Ding Gongsi) was added to 30mL of the mixture at a concentration of 4000 mg.L －1 Performing dark adsorption for 3 hours in rhodamine B solution, and measuring the absorbance of the solution by using an ultraviolet spectrophotometer, wherein the absorbance is shown as a curve 2 in fig. 4;
as a control, the concentration was measured to be 4000 mg.L using an ultraviolet spectrophotometer －1 The absorbance of rhodamine B solution, as shown in curve 1 in fig. 4;
fig. 4 is a graph showing the adsorption capacity test of a sample, wherein 1 is the absorbance of rhodamine B solution, 2 is the absorbance after dark adsorption of rhodamine B solution for 3 hours by using pure cellulose prepared by the conventional process, and 3 is the absorbance after dark adsorption of rhodamine B solution for 3 hours by using the cellulose-based photocatalytic material with weak photocatalytic performance prepared in example one;
as can be seen from fig. 4, the cellulose-based photocatalytic material with weak photocatalytic performance prepared in example one has a stronger adsorption capacity for rhodamine B, which is about 4 times that of pure cellulose prepared by using a conventional process. The contact area between the cellulose-based photocatalytic material with weak photocatalytic performance prepared in the first embodiment and the dye is increased, and more dye molecules can be adsorbed.
The light absorption capacity of the solid sample itself was tested using diffuse reflectance spectroscopy, with cellulose and carbon dioxide only absorbing in the uv range. However, the absorbance of the cellulose-based photocatalytic material with weak photocatalytic performance prepared in the first embodiment is greatly increased in the ultraviolet region and the absorbance in the visible region is improved in the full range, as shown in fig. 5;
FIG. 5 is a graph of photocatalytic efficiency, wherein 1 is pure cellulose and 2 is TiO 2 3 is absorbance of the ultraviolet light region of the cellulose-based photocatalytic material with weak photocatalytic performance prepared in the first embodiment for adsorbing rhodamine B;
as can be seen from fig. 5, the cellulose-based photocatalytic material with weak photocatalytic performance prepared in the first embodiment can perform multiple diffuse reflection, and sunlight can be repeatedly absorbed by dye molecules after multiple reflection in a rough surface, so that the utilization rate of sunlight is greatly improved.
Under the irradiation of 20 lux light intensity, 50mg of pure cellulose prepared by the traditional process is added into 30mL with the concentration of 4000 mg.L －1 Performing light absorption for 3h in rhodamine B solution, and measuring the absorbance of the solution by using an ultraviolet spectrophotometer, wherein the absorbance is shown in figure 6;
under the irradiation of 20 lux light intensity, 50mg of the cellulose-based photocatalytic material with weak photocatalytic performance prepared in the embodiment I is added into 30mL of the cellulose-based photocatalytic material with weak photocatalytic performance, and the concentration is 4000 mg.L －1 Light adsorption is carried out for 3 hours in rhodamine B solution, and the absorbance of the solution is measured by an ultraviolet spectrophotometer, and is shown in figure 7;
as can be seen from fig. 6 and 7, the catalytic efficiency of the pure cellulose prepared by the conventional process was 11.0% under the same light intensity irradiation, and the catalytic efficiency of the cellulose-based photocatalytic material with weak photocatalytic performance prepared in example one was 100%.
Coli from laboratory was used as the biological study target for 4 g.L －1 Rhodamine B solution with the concentration of 4000 mg.L －1 The plate count was performed for E.coli after culturing the aqueous solution of the cellulose-based photocatalytic material having weak photocatalytic performance (control) prepared in example one and the solution catalyzed in FIG. 7 until the degradation was completed (the degradation product of the cellulose-based photocatalytic material having weak photocatalytic performance prepared in example one).
Plate count of E.coli: bacteria with different dilution factors are respectively inoculated to the strain containing 4 g.L －1 Rhodamine B solution with the concentration of 4000 mg.L －1 The aqueous solution of the cellulose-based photocatalytic material having weak photocatalytic performance (control) prepared in example one and the solution after complete degradation (the product after degradation of the cellulose-based photocatalytic material having weak photocatalytic performance prepared in example one) prepared in FIG. 7 were cultured on LB agar medium (the concentrations of the above three solutions on LB agar medium were the same), overnight at 37℃to give a few colonies,toxicity comparison is carried out, and statistical results are recorded by photographing, and are shown in fig. 8;
FIG. 8 is a toxicity test chart.
As can be seen from FIG. 8, E.coli growth on the control was normal. Then the growth of the escherichia coli on a rhodamine B culture medium is severely inhibited, and the rhodamine B has toxic effect on the escherichia coli. The products of rhodamine B after being degraded by the sample of the patent are prepared into a culture medium with the same concentration, and the escherichia coli and a control group can be observed to show almost the same growth state. Proved by the experiment, the product after the sample is degraded has almost no toxic effect on the escherichia coli.
Claims (6)
1. A preparation method of a cellulose-based photocatalytic material with weak photocatalytic performance is characterized in that the preparation method of the cellulose-based photocatalytic material with weak photocatalytic performance is specifically completed by the following steps:
1. preparation of an aqueous cellulose solution:
(1) extracting the wood powder by using a Soxhlet extraction method by taking a mixed solution of acetic acid and sodium chlorite as a solvent;
(2) repeating the step one (1), carrying out suction filtration, and finally cleaning the solid matters obtained by suction filtration to be neutral by using distilled water to obtain solid matters A;
(3) putting the solid substance A into NaOH solution, heating, filtering, and washing the solid substance obtained by filtering with distilled water to obtain a solid substance B;
(4) firstly, immersing a solid substance B into a mixed solution of acetic acid and sodium chlorite, then heating, carrying out suction filtration, immersing the solid substance obtained by suction filtration into a NaOH solution, heating, carrying out suction filtration, and finally washing the solid substance obtained by suction filtration to be neutral by using distilled water to obtain cellulose;
the mixed solution of the acetic acid and the sodium chlorite in the step one (1) and the step one (4) is prepared by dissolving the acetic acid and the sodium chlorite into distilled water, wherein the concentration of the acetic acid is 1.3 mol/L-1.5 mol/L, and the concentration of the sodium chlorite is 0.12 mol/L-0.15 mol/L;
the concentration of the NaOH solution in the step one (3) and the step one (4) is 0.30mol/L to 0.35mol/L;
(5) adding cellulose into deionized water, and then treating by using an ultrasonic pulverizer to obtain a cellulose aqueous solution;
the mass fraction of the cellulose aqueous solution in the step one (5) is 0.1% -0.2%;
the power of the ultrasonic pulverizer in the step one (5) is 800W, and the treatment time is 30-40 min;
2. adding the photocatalytic material into a cellulose water solution, performing ultrasonic treatment, and finally performing freeze drying to obtain a cellulose-based photocatalytic material with weak photocatalytic performance;
the power of the ultrasonic wave in the second step is 650W-700W, and the ultrasonic wave time is 5 min-10 min; and in the second step, the freeze drying temperature is-40 ℃ to-50 ℃, and the freeze drying time is 20-30 hours.
2. The method for preparing a cellulose-based photocatalytic material with weak photocatalytic performance according to claim 1, wherein the extraction temperature in the step one (1) is 80-85 ℃, and the extraction time is 1-2 hours; and (3) repeating the first step (1)3-5 times) in the first step (2).
3. The method for preparing the cellulose-based photocatalytic material with weak photocatalytic performance according to claim 1, wherein in the step one (3), a solid substance A is put into a NaOH solution, heated to 75-80 ℃, treated for 1-2 hours at 75-80 ℃, suction filtered, and the solid substance obtained by suction filtration is washed by distilled water to obtain a solid substance B.
4. The method for preparing the cellulose-based photocatalytic material with weak photocatalytic performance according to claim 1, wherein in the first step (4), the solid matter B is immersed in a mixed solution of acetic acid and sodium chlorite, then heated to 80-85 ℃, treated for 1-2 hours at 80-85 ℃, subjected to suction filtration, the solid matter obtained by suction filtration is immersed in NaOH solution, treated for 1-2 hours at 80-85 ℃, and finally subjected to suction filtration, and the solid matter obtained by suction filtration is washed to be neutral by distilled water, thereby obtaining cellulose.
5. The method for preparing a cellulose-based photocatalytic material having weak photocatalytic performance according to claim 1, wherein the photocatalytic material in the second step is titanium dioxide, zinc dioxide or tin oxide; and step two, the particle size of the photocatalytic material is 100 nm-1000 nm.
6. The method for preparing the cellulose-based photocatalytic material with weak photocatalytic performance according to claim 1, wherein the mass fraction of the photocatalytic material in the cellulose-based photocatalytic material with weak photocatalytic performance in the second step is 25% -30%.
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| CN102899949A (en) * | 2012-08-10 | 2013-01-30 | 襄垣县鑫瑞达连氏塑木制造有限公司 | Method for preparing cellulose nano-fibril film by utilizing wood powder |
| CN103387689A (en) * | 2013-08-19 | 2013-11-13 | 南京林业大学 | Method for preparing nanocellulose fiber optical transparent membrane material from peanut hulls |
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| CN102899949A (en) * | 2012-08-10 | 2013-01-30 | 襄垣县鑫瑞达连氏塑木制造有限公司 | Method for preparing cellulose nano-fibril film by utilizing wood powder |
| CN103387689A (en) * | 2013-08-19 | 2013-11-13 | 南京林业大学 | Method for preparing nanocellulose fiber optical transparent membrane material from peanut hulls |
| CN108355717A (en) * | 2018-01-16 | 2018-08-03 | 齐鲁工业大学 | A kind of preparation method of cellulose/BiOBr composite photocatalyst materials |
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