CN111617740A - Layered carbon/titanium dioxide composite material and preparation method and application thereof - Google Patents
Layered carbon/titanium dioxide composite material and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 239000002028 Biomass Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
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- 239000012298 atmosphere Substances 0.000 claims description 5
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- 230000001681 protective effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 16
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- 230000009286 beneficial effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
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- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 230000006872 improvement Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The invention relates to a layered carbon/titanium dioxide composite material and a preparation method and application thereof, wherein the composite material is prepared by adopting the following preparation method: s1: adding a biomass raw material into glacial acetic acid for hydrothermal reaction to obtain layered carbon; s2: preparing titanium dioxide by taking tetrabutyl titanate as a raw material through a solvothermal method; s3: adding titanium dioxide into an ethanol solution for ultrasonic treatment, adding layered carbon for continuous ultrasonic treatment to obtain layered carbon/titanium dioxide, and calcining the layered carbon/titanium dioxide to obtain a layered carbon/titanium dioxide composite material; the composite material can be applied to the field of organic wastewater treatment. The titanium dioxide composite material has high titanium dioxide loading rate and large specific surface area, and the removal rate of phenol under visible light can reach 89.60%.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a layered carbon/titanium dioxide composite material and a preparation method and application thereof.
Background
The phenol pollutants have the characteristics of wide distribution area, strong toxicity, poor biodegradability and the like, and cause serious harm to human health and ecological system balance. Therefore, the research and development of the efficient and environment-friendly wastewater treatment agent have important significance for environmental protection.
The biomass charcoal has the characteristics of wide raw material source, low preparation cost, environmental friendliness, good stability and the like, and has attracted people's attention, but the traditional biomass charcoal has poor adsorption performance and limited use in wastewater treatment. The photocatalyst is also a wastewater treatment agent which is of great interest, and can finally degrade organic pollutants into carbon dioxide, water and some nontoxic and harmless small molecular substances under the action of illumination, but the defects of weak adsorption capacity and low light utilization rate of the photocatalyst greatly limit the application of the photocatalyst in practice.
Based on the advantages, the novel wastewater treatment agent which combines the advantages of the biomass charcoal and the photocatalyst and can overcome the defects of two materials has important significance.
Disclosure of Invention
Aiming at the technical problems of poor adsorption performance, weak adsorption capacity of a photocatalyst and low light utilization rate of the traditional biomass carbon, the invention provides a layered carbon/titanium dioxide composite material and a preparation method and application thereof.
In a first aspect, the present invention provides a process for preparing a layered carbon/titanium dioxide composite material, said process comprising the steps of:
s1: adding a biomass raw material into glacial acetic acid, uniformly mixing, transferring to a high-pressure reaction kettle for hydrothermal reaction, centrifuging, cleaning, drying and grinding after the reaction is finished, adding the ground powder into an ethanol solution, and performing ultrasonic treatment, drying and grinding to obtain layered carbon;
s2: preparing titanium dioxide by taking tetrabutyl titanate as a raw material through a solvothermal method;
s3: adding titanium dioxide into an ethanol solution, performing ultrasonic dispersion uniformly, adding layered carbon, performing continuous ultrasonic treatment, centrifuging, drying and grinding to obtain layered carbon/titanium dioxide, and calcining the layered carbon/titanium dioxide in a protective gas atmosphere to obtain the layered carbon/titanium dioxide composite material.
Further, S1 includes the following steps:
adding 3g of biomass raw material into 60mL of glacial acetic acid, uniformly mixing, transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction for 6h at 150 ℃, centrifuging, cleaning, drying and grinding after the reaction is finished, adding the ground powder into an ethanol solution, and carrying out ultrasonic treatment, drying and grinding to obtain the layered carbon.
Further, S2 includes the following steps:
s21: uniformly mixing tetrabutyl titanate and absolute ethyl alcohol according to the volume ratio of 1: 1;
s22: according to the weight ratio of absolute ethyl alcohol: 1 part of water: weighing absolute ethyl alcohol according to a volume ratio of 0.5, uniformly mixing the absolute ethyl alcohol and water to obtain an ethanol solution, wherein the volume of the absolute ethyl alcohol is the same as that of the absolute ethyl alcohol in S21, dropwise adding the S21 solution into the ethanol solution, continuously stirring for 30min, and adjusting the pH value of the solution to 7 to obtain a precursor solution;
s23: transferring the precursor solution into a reaction kettle, carrying out hydrothermal reaction at 240 ℃ for 19h, and naturally cooling to room temperature after the reaction is finished;
s24: and centrifuging, washing, drying and grinding the hydrothermal product to obtain the titanium dioxide.
Further, S3 includes the following steps:
adding titanium dioxide into an ethanol solution, and after uniformly dispersing by ultrasonic, adding titanium dioxide: adding layered carbon in a mass ratio of 1:5, continuing to perform ultrasonic treatment, centrifuging, drying and grinding to obtain layered carbon/titanium dioxide, heating the layered carbon/titanium dioxide to 800 ℃ under the atmosphere of protective gas, and calcining for 2 hours to obtain the layered carbon/titanium dioxide composite material.
Further, the calcination temperature of S3 was 800 ℃.
Further, the temperature increase rate of S3 was 5 ℃/min.
In a second aspect, the invention provides a layered carbon/titanium dioxide composite material prepared by the preparation method.
In a third aspect, the invention provides an application of the layered carbon/titanium dioxide composite material prepared by the preparation method in organic wastewater treatment.
Further, the organic wastewater is phenol wastewater.
Further, the application method is that the layered carbon/titanium dioxide composite material is uniformly dispersed in phenol wastewater, and phenol is degraded by visible light catalysis.
The beneficial effect of the invention is that,
according to the layered carbon/titanium dioxide composite material and the preparation method and application thereof, glacial acetic acid is adopted to treat a biomass raw material to prepare the layered carbon, the glacial acetic acid destroys oxygen bonds among cellulose of the biomass raw material, large cellulose is stripped into a flaky structure, and the specific surface area of the carbon is increased; the preparation method and parameters of the titanium dioxide are limited, and the spheroidal nano titanium dioxide with similar particle size and the diameter of about 20nm is successfully prepared; the layered carbon and the titanium dioxide are compounded by the process of firstly compounding by ultrasonic and then calcining at high temperature, the prepared composite material has high titanium dioxide loading rate and large specific surface area, and the removal rate of phenol under visible light can reach 89.60 percent.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of the delaminated carbon and the leaf carbon prepared in example 1 at a magnification of 1 Ktimes;
FIG. 2 is a TEM photograph of the titanium dioxide prepared in example 2 at 6 ten thousand times and 60 ten thousand times;
FIG. 3 is an X-ray diffraction pattern of titanium dioxide prepared in example 2;
FIG. 4 is a scanning electron micrograph and an X-ray energy spectrum of the layered carbon/titanium dioxide composite materials prepared in example 3 and comparative example 1;
FIG. 5 is a thermogravimetric plot of the layered carbons prepared in example 1, the layered carbon/titania composites prepared in examples 3-4, and comparative examples 1-2;
FIG. 6 is a bar graph of the removal efficiency of P25, titanium dioxide prepared in example 2, layered carbon/titanium dioxide composites prepared in examples 3-4 and comparative examples 1-2 to phenol in visible light.
In the figure, LC is layered carbon, BC is leaf carbon, TiO2Is the titanium dioxide, and the titanium dioxide,
TiO2the/LC-800 is a layered carbon/titanium dioxide composite material prepared by ultrasonically compounding titanium dioxide and layered carbon and then calcining at 800 ℃;
TiO2the/LC-500 is a layered carbon/titanium dioxide composite material prepared by ultrasonically compounding titanium dioxide and layered carbon and then calcining at 500 ℃;
TiO2the 800-LC is a layered carbon/titanium dioxide composite material prepared by calcining layered carbon at 800 ℃ and then ultrasonically compounding the layered carbon with titanium dioxide
TiO2the/500-LC is a layered carbon/titanium dioxide composite material prepared by calcining layered carbon at 500 ℃ and then ultrasonically compounding the layered carbon with titanium dioxide.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all 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.
EXAMPLE 1 preparation of layered carbon
The layered carbon uses leaves as a biomass raw material, and is firstly pretreated by cleaning, drying and crushing the leaves before use, and the specific preparation method of the layered carbon comprises the following steps:
adding 3g of biomass raw material into 60mL of glacial acetic acid, uniformly mixing, transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction for 6h at 150 ℃, centrifuging, cleaning, drying and grinding after the reaction is finished, adding the ground powder into an ethanol solution, and carrying out ultrasonic treatment, drying and grinding to obtain the layered carbon LC.
EXAMPLE 2 preparation of titanium dioxide
According to the volume ratio of the reaction system temperature (T), the reaction time (T) and the tetrabutyl titanate to the ethanol
Volume ratio of tetrabutyl titanate to water
The pH of the precursor solution is a research object, and 25 groups of L with 5 factors and 5 levels are designed25And (3) performing an orthogonal test, namely performing a photocatalytic test on the prepared titanium dioxide, screening a titanium dioxide material with good photocatalytic performance by taking the degradation rate η of phenol as an index, and determining an optimal preparation method of the titanium dioxide, wherein the orthogonal test table is shown in the following table 1.
Table 1 orthogonal test table
The preparation method of the titanium dioxide comprises the following steps:
(1) according to
Respectively weighing tetrabutyl titanate and absolute ethyl alcohol according to the proportion, mixing tetrabutyl titanate and half of absolute ethyl alcohol, stirring for 30min by using a magnetic stirrer, and uniformly mixing;
(2) according to
Taking water according to the proportion, preparing ethanol solution from the remaining half of ethanol and water, dropwise adding the solution obtained in the step (1) into the ethanol solution under magnetic stirring, continuously stirring for 30min, and adding 1M HNO3Or NH3·H2Adjusting the pH value of the solution to obtain a precursor solution;
(3) transferring the precursor solution into a reaction kettle, carrying out hydrothermal reaction for T time at the temperature T, and naturally cooling to room temperature after the reaction is finished;
(4) and centrifuging the hydrothermal product to obtain a white precipitate, washing the white precipitate for several times by using distilled water and absolute ethyl alcohol until the filtrate is neutral, drying the white precipitate at 80 ℃, and grinding to obtain the titanium dioxide.
The photocatalytic experiment of titanium dioxide comprises the following steps:
(1) 160mL of 50mg/L phenol solution was taken and the initial absorbance A at 270nm was measured using an ultraviolet-visible spectrophotometer0；
(2) Adding 0.08g of prepared titanium dioxide powder into a phenol solution, and performing ultrasonic treatment for 10min to rapidly and uniformly disperse the titanium dioxide powder in the phenol solution;
(3) placing the phenol solution in a reactor for dark reaction for 30min to ensure that the material reaches adsorption equilibrium;
(4) turning on a xenon lamp light source, filtering the light source with the wavelength of more than 420mm, enabling the distance between the light source and the upper end of the solution to be 12cm, enabling the illumination time to be 120min, sampling every 30min, obtaining supernatant through centrifugation, measuring the absorbance At of the supernatant At 270nm by using an ultraviolet spectrophotometer, and calculating the degradation rate eta of phenol, wherein the calculation formula is as follows:
η(％)＝(A0-At)/A0×100％。
the results of the orthogonal test and the range analysis are shown in tables 2 and 3 below.
TABLE 2 orthogonal test results Table
TABLE 3 range analysis table
As can be seen from Table 3, the sequence of the influence of each factor on the photocatalytic performance of the nano titanium dioxide material is as follows: temperature T of reaction system>Reaction time
The pH of the precursor solution, namely the hydrothermal reaction temperature T, has the greatest influence on the photocatalytic performance in the preparation process of the nano titanium dioxide material. According to the analysis of 25 groups of orthogonal test results, the optimal horizontal combination is that the temperature of a reaction system is 240 ℃, the reaction time is 19h,
the precursor solution had a pH of 7.
Titanium dioxide is prepared according to the optimal level combination, and an ultraviolet light catalysis experiment is carried out, so that the degradation rate of the titanium dioxide to phenol is determined to be 94.10%.
EXAMPLE 3 composite of layered carbon with titanium dioxide
A layered carbon/titanium dioxide composite material, wherein the layered carbon is the layered carbon prepared in example 1, and the titanium dioxide is the titanium dioxide prepared in example 2 by combining the layered carbon and the titanium dioxide at an optimum level, and the method for compounding the layered carbon and the titanium dioxide comprises the following steps:
adding titanium dioxide into an ethanol solution, and after uniformly dispersing by ultrasonic, adding titanium dioxide: 1, layered carbon: 5, adding layered carbon, continuing to perform ultrasonic treatment for 2 hours, centrifuging to obtain a precipitate, drying at 80 ℃, grinding to obtain layered carbon/titanium dioxide, heating the layered carbon/titanium dioxide to 800 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and calcining for 2 hours to obtain a layered carbon/titanium dioxide composite material TiO2/LC-800。
EXAMPLE 4 composite of layered carbon with titanium dioxide
Example 4 differs from example 3 in that,example 4 calcination temperature was 500 ℃ and the resulting layered carbon/titanium dioxide composite was designated TiO2/LC-500。
Comparative example 1
A layered carbon/titanium dioxide composite material, wherein the layered carbon is the layered carbon prepared in example 1, and the titanium dioxide is the titanium dioxide prepared in example 2 by combining the layered carbon and the titanium dioxide at an optimum level, and the method for compounding the layered carbon and the titanium dioxide comprises the following steps:
heating the layered carbon to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining for 2h, adding titanium dioxide into an ethanol solution, uniformly dispersing, and then adding titanium dioxide: 1, layered carbon: 5, adding calcined layered carbon, continuing to perform ultrasonic treatment for 2 hours, centrifuging to obtain a precipitate, drying at 80 ℃, and grinding to obtain the layered carbon/titanium dioxide composite material TiO2/800-LC。
Comparative example 2
Comparative example 2 differs from comparative example 1 in that the calcination temperature of comparative example 2 is 500 deg.C and the resulting layered carbon/titanium dioxide composite is designated TiO2/500-LC。
Test example 1 characterization of layered carbon
The layered carbon obtained in example 1 was characterized by its morphology using a Scanning Electron Microscope (SEM), and the same procedure was used to prepare leaf carbon without glacial acetic acid. It can be seen from fig. 1 that the layered carbon added with glacial acetic acid is flaky, and the leaf carbon not added with glacial acetic acid is massive, which indicates that the treatment of glacial acetic acid can peel the massive carbon into flaky form, which is beneficial to the improvement of the specific surface area of the carbon and the acceleration of the charge transfer speed, and further influences the photocatalytic performance of the treatment.
Test example 2 characterization of titanium dioxide
The titanium dioxide obtained in example 2 was characterized by a Transmission Electron Microscope (TEM) and an X-ray diffractometer (XRD).
(1) TEM analysis
As can be seen from FIG. 2, the titanium dioxide is spherical-like and has similar particle sizes, and the mutually staggered lattice stripes can be clearly seen on the surface of the titanium dioxide, and the measured lattice spacing is about 0.347nm, which corresponds to the (101) crystal face of the anatase phase.
(2) XRD analysis
As can be seen from FIG. 3, the titanium dioxide prepared in example 2 is a typical anatase phase, and compared with a standard card (JCPDS No.89-4921), the diffraction peak types are all sharp, which shows that the crystallinity is higher, the crystal lattice defects are fewer, and the conduction of carriers and the photocatalytic activity of the catalyst are facilitated.
Test example 3 characterization of layered carbon/titanium dioxide composite
The layered carbon/titanium dioxide composite material was characterized by Scanning Electron Microscope (SEM), X-ray energy spectrometer (EDS), thermogravimetric analyzer (TGA), and the specific surface area (BET) and Pore Size Distribution (PSD) of the layered carbon/titanium dioxide composite material were determined.
(1) SEM and EDS analysis
As can be seen from FIG. 4, the TiO produced in example 32TiO from/LC-800 and comparative example 12Granular substances exist on the surface of the/800-LC layered carbon, which indicates that titanium dioxide is successfully loaded on the surface of the layered carbon, and the EDS also detects the existence of Ti element.
(2) TGA analysis
FIG. 5 is a thermogravimetric analysis of the layered carbon and the layered carbon/titanium dioxide composite calcined at 25 ℃ to 800 ℃ in the air atmosphere, as shown in FIG. 5, the weight loss of the LC calcined at 800 ℃ in the air is 99.9%, so the calcined weight of the layered carbon can be ignored in the thermogravimetric analysis of the layered carbon/titanium dioxide composite, and the TiO is obtained by calculation2/LC-800、TiO2/LC-500、TiO2/800-LC、TiO2The titanium dioxide proportions in the/500-LC were 45.05%, 34.83%, 23.44% and 29.05%, respectively. Comparing the proportions of the titanium dioxide in the composite materials can conclude that the composite material prepared by the method of firstly carrying out ultrasonic compounding and then carrying out high-temperature calcination has higher titanium dioxide loading rate, and the high calcination temperature is beneficial to the loading of the titanium dioxide.
(3) BET and PSD analysis
Specific surface area and pore structure parameters of the layered carbon/titanium dioxide composites prepared in examples 3 to 4 and comparative example 1 were measured, and LC-800 obtained by calcining the layered carbon prepared in example 1 at a heating rate of 5 ℃/min up to 800 ℃ for 2 hours in a nitrogen atmosphere was used as a control, and the measurement results are shown in table 4 below.
TABLE 4 specific surface area and pore Structure parameters
As can be seen from Table 4, the specific surface area of the material is reduced after loading titanium dioxide, because the titanium dioxide loading can block part of the pore channels of the carbon; comparative example 3TiO2Per LC-800 and comparative example 1TiO2The two materials of/800-LC are found that the specific surface area of the material which is subjected to ultrasonic compounding and then high-temperature calcination is higher; comparative example 3TiO2Per LC-800 and example 4TiO2The two materials of/LC-500 show that the increase of the calcination temperature is beneficial to the increase of the specific surface area and the pore volume of the composite material.
Test example 4 testing of phenol removal Performance of layered carbon/titanium dioxide composites under visible light
The method for testing the performance of the composite material in removing phenol under visible light comprises the following steps:
(1) 0.02g of the material prepared in examples 2-5 and comparative examples 1-2 and the commercial P25 titanium dioxide material were added to 40mL of a 50mg/L phenol solution, and the mixture was subjected to ultrasonic treatment for 10min to rapidly and uniformly disperse the material in the phenol solution;
(2) placing the mixed solution in a reactor for dark reaction for 30min to ensure that the material reaches adsorption balance;
(3) turning on xenon lamp light source, filtering light source with wavelength below 420nm, irradiating for 240min with light source 12cm away from the upper end of the solution;
(4) centrifuging to obtain supernatant, measuring absorbance of the supernatant at 270nm by using an ultraviolet-visible spectrophotometer, and calculating the degradation rate eta of phenol by using the same calculation formula as that in example 2.
As shown in FIG. 6, the removal of titanium dioxide prepared in example 2 is superior to commercial product P25 when a phenol solution is treated under visible light conditions for 4 hours, indicating that the nano-scale size of titanium dioxide prepared in example 2 provides a larger ratio tableThe area is more beneficial to the contact with phenol molecules; comparative examples 1 and 2 TiO prepared by high temperature calcination followed by ultrasonic compounding method2800-LC and TiO2The improvement of phenol removal efficiency of the 500-LC is not obvious compared with that of the embodiment 2; examples 3-4 TiO prepared by ultrasonic compounding followed by high temperature calcination2/LC-800 and TiO2The phenol removal effect of the/LC-500 is better than that of the comparative examples 1-2 and the example 2, the increase of the calcination temperature is beneficial to the improvement of the phenol removal effect, and the example 3 is that TiO calcined at 800 ℃ is subjected to ultrasonic compounding firstly and then subjected to the calcination2The best effect of removing phenol is achieved by/LC-800, the removal rate is 89.60%, which is in accordance with TiO2The larger specific surface area of/LC-800 relates to more titanium dioxide loading.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the layered carbon/titanium dioxide composite material is characterized by comprising the following steps:
s1: adding a biomass raw material into glacial acetic acid, uniformly mixing, transferring to a high-pressure reaction kettle for hydrothermal reaction, centrifuging, cleaning, drying and grinding after the reaction is finished, adding the ground powder into an ethanol solution, and performing ultrasonic treatment, drying and grinding to obtain layered carbon;
s2: preparing titanium dioxide by taking tetrabutyl titanate as a raw material through a solvothermal method;
s3: adding titanium dioxide into an ethanol solution, performing ultrasonic dispersion uniformly, adding layered carbon, performing continuous ultrasonic treatment, centrifuging, drying and grinding to obtain layered carbon/titanium dioxide, and calcining the layered carbon/titanium dioxide in a protective gas atmosphere to obtain the layered carbon/titanium dioxide composite material.
2. The method of claim 1, wherein S1 comprises the steps of:
adding 3g of biomass raw material into 60mL of glacial acetic acid, uniformly mixing, transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction for 6h at 150 ℃, centrifuging, cleaning, drying and grinding after the reaction is finished, adding the ground powder into an ethanol solution, and carrying out ultrasonic treatment, drying and grinding to obtain the layered carbon.
3. The method of claim 1, wherein S2 comprises the steps of:
s21: uniformly mixing tetrabutyl titanate and absolute ethyl alcohol according to the volume ratio of 1: 1;
s22: according to the weight ratio of absolute ethyl alcohol: 1 part of water: weighing absolute ethyl alcohol according to a volume ratio of 0.5, uniformly mixing the absolute ethyl alcohol and water to obtain an ethanol solution, wherein the volume of the absolute ethyl alcohol is the same as that of the absolute ethyl alcohol in S21, dropwise adding the S21 solution into the ethanol solution, continuously stirring for 30min, and adjusting the pH value of the solution to 7 to obtain a precursor solution;
s23: transferring the precursor solution into a reaction kettle, carrying out hydrothermal reaction at 240 ℃ for 19h, and naturally cooling to room temperature after the reaction is finished;
s24: and centrifuging, washing, drying and grinding the hydrothermal product to obtain the titanium dioxide.
4. The method of claim 1, wherein S3 comprises the steps of:
adding titanium dioxide into an ethanol solution, and after uniformly dispersing by ultrasonic, adding titanium dioxide: adding layered carbon in a mass ratio of 1:5, continuing to perform ultrasonic treatment, centrifuging, drying and grinding to obtain layered carbon/titanium dioxide, heating the layered carbon/titanium dioxide to 800 ℃ under the atmosphere of protective gas, and calcining for 2 hours to obtain the layered carbon/titanium dioxide composite material.
5. The method according to claim 4, wherein the calcination temperature of S3 is 800 ℃.
6. The method according to claim 4, wherein the temperature increase rate of S3 is 5 ℃/min.
7. A layered carbon/titanium dioxide composite material produced by the production method according to any one of claims 1 to 6.
8. Use of the layered carbon/titanium dioxide composite of claim 7 in organic wastewater treatment.
9. The use of claim 8, wherein the organic waste water is phenol waste water.
10. The use of claim 9, wherein the layered carbon/titanium dioxide composite is used by dispersing the layered carbon/titanium dioxide composite uniformly in phenol wastewater to degrade phenol with visible light catalysis.
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