CN115888677B - Method for preparing carbon-titanium dioxide nano composite porous photocatalyst - Google Patents
Method for preparing carbon-titanium dioxide nano composite porous photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 title claims abstract description 31
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000006228 supernatant Substances 0.000 claims abstract description 42
- 229910021538 borax Inorganic materials 0.000 claims abstract description 36
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 36
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 36
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229960003638 dopamine Drugs 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 8
- 238000000703 high-speed centrifugation Methods 0.000 claims description 5
- 238000000464 low-speed centrifugation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 244000144992 flock Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 14
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- 239000004408 titanium dioxide Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000001782 photodegradation Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 241000219000 Populus Species 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229920001690 polydopamine Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241001412225 Firmiana simplex Species 0.000 description 4
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- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 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 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
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- 238000004887 air purification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 206010016256 fatigue Diseases 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000877 morphologic 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
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- 239000005871 repellent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to the technical field of nano photocatalytic materials, in particular to a method for preparing a carbon-titanium dioxide nano composite porous photocatalyst. S1, treating flying cotton wool, centrifuging at a high speed to remove liquid, adjusting pH, centrifuging at a low speed, and taking supernatant; s2, taking the supernatant fluid obtained in the step S1, adding borax solution under stirring, then dropwise adding calcium nitrate solution, keeping stirring, adding dopamine powder, centrifuging to remove liquid, and then cleaning to obtain powder; s3, dispersing the powder prepared in the step S2 in an organic solvent, adding ethyl titanate to react under stirring, centrifuging, drying, calcining without oxygen, and then pickling to obtain a target product.
Description
Technical Field
The invention relates to the technical field of nano photocatalytic materials, in particular to a method for preparing a carbon-titanium dioxide nano composite porous photocatalyst.
Background
TiO 2 is a novel photocatalyst capable of driving photocatalytic water-borne organic substances, and among many photocatalysts, tiO 2 has characteristics of stable performance, water-insoluble property, no toxicity, high catalytic activity and the like, and is an excellent photocatalyst which has been paid attention in recent years. The nanoscale TiO 2 has been of great interest to researchers because of its unique structure and properties, but its wide bandgap and rapid recombination of photogenerated electrons limit practical applications.
At present, the preparation method of the nano TiO 2 mainly comprises a hydrothermal method, a solvothermal method, a sol-gel method and the like, and the preparation method often needs harsh preparation conditions or expensive or toxic raw materials, so that the requirement of industrial mass production cannot be met, and the application prospect of the nano TiO 2 is greatly limited.
Naturally occurring substances in nature often have some perfect functional properties, often resulting from the unique functional natural structure they possess. Accordingly, the synthesis of nano TiO 2 using biology as a template has been widely studied. The method is characterized in that the flying catkin such as poplar wadding, willow wadding and phoenix tree wadding is used as natural carbon skeleton fiber resources, the specific surface area is relatively high, for example, the length of the poplar wadding fiber is about 5mm, the diameter of the poplar wadding fiber is about 10.5 mu m (Yin Chuanqing, zhang Hongting, the morphological structure and application of the poplar wadding fiber are [ J ], shandong spinning economy and 2013 (9); 37-38,89) and is suitable for being used as a substrate to prepare nano TiO 2 materials, for example, chinese patent document CN 106311196A (application number 201610578035.2) discloses a tubular structure nano titanium dioxide photocatalyst and a preparation method.
Therefore, a method for preparing the nano TiO 2 photocatalytic material by utilizing the flying cotton is needed to meet the actual production requirement.
Disclosure of Invention
The invention aims to solve the technical problems and provide a method for preparing a carbon-titanium dioxide nano composite porous photocatalyst, wherein flying cotton fiber and borate are used as templates, dopamine (DA) is used as a connecting agent, so that titanium dioxide can be uniformly dispersed on the surfaces of the templates, and meanwhile, no pollutant is generated in the used materials, and the preparation method is environment-friendly and convenient for industrial mass production.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a method of preparing a carbon-titania nanocomposite porous photocatalyst comprising the steps of:
S1, soaking the fly wadding with alkali liquor after cleaning, centrifuging at a high speed to remove liquid, adjusting pH, centrifuging at a low speed, and taking supernatant;
S2, taking the supernatant fluid obtained in the step S1, adding borax solution under stirring, then dropwise adding calcium nitrate solution, keeping stirring, adding dopamine powder, centrifuging to remove liquid, and then cleaning to obtain powder;
S3, dispersing the powder prepared in the step S2 in an organic solvent, adding ethyl titanate to react under stirring, centrifuging, drying, calcining without oxygen, and then pickling to obtain a target product.
According to the preparation method provided by the invention, the carbon skeleton fiber structure of the flying cotton and the borate are used as templates, the purpose of adding the borate as a second template is to increase the dispersibility and specific surface area of the prepared TiO 2 on the basis of taking the flying cotton fiber structure as a first template, and the dopamine is used as a connecting agent, so that the generated titanium dioxide can be uniformly dispersed on the surface of the templates, and after sintering, the borate is still in powder, and the borate is removed by acid washing, so that the mass ratio of the titanium dioxide in the product is improved, and the catalytic effect of the photocatalyst with the same mass is effectively improved.
Preferably, in the step S1, the flying cotton wool is specifically soaked in alkali liquor after being cleaned.
Preferably, in the step S1, the ratio of the mass of the thrown-in fly wadding to the supernatant taken out is 0.2-0.8 g/1 mL.
Preferably, in the step S1, the alkali in the alkali solution is selected from NaOH, KOH or Ca (OH) 2, the pH value of the alkali solution is 8.0-11.0, and the soaking time of the alkali solution is 10-36h; more preferably, the pH of the alkaline solution is 9.0-10.0, and the alkaline solution soaking time is 12-24 hours.
Preferably, in the step S1, the pH is adjusted to 7.5-8.5 by adding distilled water; more preferably, the pH is adjusted to 7.5-8.0.
Preferably, in the step S1, the rotating speed of the high-speed centrifugation is 2000-4000r/min, and the rotating speed of the low-speed centrifugation is 200-800r/min; more preferably, the high-speed centrifugation has a rotational speed of 2500-3500r/min and the low-speed centrifugation has a rotational speed of 300-500r/min.
In the step S1, firstly, the flyball is cleaned to remove the water-repellent impurities on the surface, and the alkali liquor is used for soaking and extracting carbon skeleton fibers in the flyball, and simultaneously, the surface of the carbon skeleton fibers is modified to enable the carbon skeleton fibers to have the binding capacity to be used as a template, firstly, the excess alkali liquor is removed by high-speed centrifugation, then the alkali liquor is washed away and the pH value is regulated, and finally, the flyball which is hydroxylated and well dispersed is dispersed in the supernatant by low-speed centrifugation, so that the flyball is convenient to take out for subsequent reaction.
Preferably, in the step S2, the volume ratio of the borax solution to the supernatant is 0.1-0.5:1, the borax concentration in the borax solution is 0.1-1mol/L, and the amount of the borax contained in the borax solution and the amount of the calcium nitrate contained in the calcium nitrate solution are the same; more preferably, the volume ratio of the borax solution to the supernatant is 0.1-0.2:1, and the borax concentration in the borax solution is 0.2-0.6mol/L.
Preferably, in the step S2, the ratio of the mass of the dopamine powder to the volume of the supernatant is 0.01-0.05 g/1 mL; more preferably, the ratio of the mass of dopamine powder charged to the volume of supernatant is 0.015-0.03 g/1 mL.
Preferably, in the step S2, the stirring rotation speed is 200-800r/min, and the centrifugal rotation speed is 2000-3000r/min; more preferably, the stirring speed is 300-500r/min and the centrifugal speed is 2200-2500r/min.
Preferably, in the step S2, the washing method is to use distilled water and absolute ethanol to alternately wash.
In the step S2, borax solution and calcium nitrate solution are respectively added, template agent borate is generated in carbon skeleton fiber gaps under the stirring condition, then dopamine is added, self-polymerization reaction is carried out on the dopamine under the slightly alkaline environment, polydopamine is generated and is used as a connecting agent to be attached to the surfaces of the flybatting and the borate, and the template substance with the connecting agent polydopamine is obtained after the unattached borax, calcium nitrate and dopamine are removed through cleaning.
Preferably, in the step S3, the organic solvent is selected from one of absolute ethanol, propanol, acetone or other organic solvents.
Preferably, in the step S3, the ratio of the volume of the ethyl titanate added to the volume of the supernatant is 0.1-0.8:1; more preferably, the ratio of the volume of ethyl titanate charged to the volume of supernatant is 0.2-0.5:1.
Preferably, in the step S3, after adding ethyl titanate, the reaction time is 10-36 hours; more preferably, the reaction time is 20 to 24 hours.
Preferably, in the step S3, the stirring speed is 100-300r/min, the stirring time is 12-24 hours, and the centrifugal speed is 2000-3000r/min; more preferably, the stirring speed is 2500-2700r/min, the stirring time is 15-20 hours, and the centrifugal speed is 2200-2500r/min.
Preferably, in the step S3, the temperature of the anaerobic calcination is 200-800 ℃, and the duration of the anaerobic calcination is 0.2-0.5 hours; more preferably, the temperature of the anaerobic calcination is 400-600 ℃, and the duration of the anaerobic calcination is 0.3-0.5 hours.
Preferably, in the step S3, the acid solution used for acid washing is selected from dilute hydrochloric acid, acetic acid or nitric acid, and the pH of the acid solution is 1.0-3.0; more preferably, the acid used for the acid washing is selected from dilute hydrochloric acid, and the pH of the acid is 1.0-2.0.
In the step S3, an organic solvent is used as a reaction medium, titanium dioxide precursor ethyl titanate is added for stirring, the formed titanium dioxide is adhered to the surface of polydopamine, the titanium dioxide in the obtained product can be effectively dispersed by limiting the proportion relation between the ethyl titanate and the supernatant, the excessive reaction medium is removed by centrifugation and drying, the polydopamine and the fiber are carbonized in the anaerobic calcining process, the acid liquor is used for cleaning, and the borate is removed, so that the target product carbon-titanium dioxide nano composite porous photocatalyst can be obtained. At high temperature, polydopamine is carbonized, heteroatom N and carbon skeleton fiber are simultaneously introduced for doping, and the nitrogen hybridized carbon material is a nontoxic nonmetallic semiconductor material, has the advantages of a two-dimensional layered structure, good chemical stability and the like, so that nitrogen hybridization is applied to the fields of environmental purification, including air purification, wastewater restoration and the like [ Qin Zemin ], development of uranium removal by photocatalytic reduction of graphite-phase carbon nitride-based materials [ J/OL ]. Silicate report, https:// doi.org/10.16552/j.cnki.issn1001-1625.20221012.001]. The catalytic efficiency of the photocatalyst is further improved through high-temperature anaerobic sintering.
The invention also provides the carbon-titanium dioxide nano composite porous photocatalyst prepared by the method, and the photocatalyst consists of an nitrogen hybridized carbon skeleton and titanium dioxide coated outside the skeleton.
The beneficial effects of the invention are as follows:
1. The invention provides a method for preparing a carbon-titanium dioxide nano-composite porous photocatalyst by taking fly-wadding fibers and borate as templates and dopamine as a connecting agent, so that titanium dioxide can be uniformly dispersed on the surfaces of the templates, and meanwhile, the used materials can not produce pollutants, and the preparation method is environment-friendly and convenient for industrial mass production.
2. According to the preparation method provided by the invention, the carbon material, the washed-out borate and the titanium dioxide are prepared respectively through sintering and acid washing, so that the mass ratio of titanium dioxide in the photocatalyst is effectively improved, and the catalytic effect of the photocatalyst with unit mass is effectively improved.
3. According to the invention, by limiting the feeding proportion relation between the titanium dioxide precursor and the supernatant, titanium dioxide in the prepared photocatalyst is effectively dispersed, and the photocatalyst has a good catalytic effect;
4. According to the preparation method provided by the invention, through high-temperature sintering, the polydopamine and the carbon skeleton fiber form a nitrogen-doped carbon structure, so that the catalytic efficiency of the photocatalyst is further improved.
Drawings
FIG. 1 is an SEM image of a carbon-titania nanocomposite porous photocatalyst prepared in example 1;
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples.
Example 1:
A method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst, in this example, poplar wadding is used as a template, specifically comprising the following steps:
S1, adding 15.0g of poplar cotton wool, washing the poplar cotton wool with distilled water and absolute ethyl alcohol to remove impurities on the surface of the poplar cotton wool, soaking the poplar cotton wool in a NaOH solution with the pH value of 10.0 for 24 hours, centrifuging at a high speed of 3000r/min to remove liquid, adding distilled water to adjust the pH value to 7.5, and centrifuging at a low speed of 200r/min to obtain 30mL of supernatant;
S2, taking supernatant fluid obtained in the step S1, adding borax solution under stirring at a rotating speed of 250r/min, then dropwise adding calcium nitrate solution, wherein the concentration of the borax solution is 0.2mol/L, the volume ratio of the borax solution to the supernatant fluid is 0.2:1, the borax contained in the added borax solution is the same as the substances of calcium nitrate contained in the calcium nitrate solution, dopamine powder is kept stirring, the volume ratio of the added dopamine powder to the supernatant fluid is 0.02g:1mL, and after liquid is removed by centrifugation, distilled water and absolute ethyl alcohol are used for alternately cleaning to obtain powder;
S3, dispersing the powder prepared in the step S2 in 20mL of absolute ethyl alcohol, adding ethyl titanate under stirring at a rotating speed of 300r/min for reaction for 24 hours, adding a ratio of the volume of the ethyl titanate to the volume of supernatant fluid of 0.2:1, centrifuging at a rotating speed of 2000r/min to remove liquid, drying, calcining at 600 ℃ for 0.5 hour under an anaerobic condition in a tubular furnace, and pickling with dilute hydrochloric acid with a pH value of 1.0 to obtain a target product.
Example 2:
a method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst, in this embodiment, catkin is used as a template, and specifically comprises the following steps:
S1, adding 8.0g of catkin, washing with distilled water and absolute ethyl alcohol to remove impurities on the surface of the catkin, soaking the catkin in KOH solution with the pH value of 9.0 for 20 hours, centrifuging at a high speed of 3000r/min to remove liquid, adding distilled water to adjust the pH value to 7.8, and centrifuging at a low speed of 200r/min to obtain 20mL of supernatant;
s2, taking supernatant fluid obtained in the step S1, adding borax solution under stirring at a rotating speed of 200r/min, then dropwise adding calcium nitrate solution, wherein the concentration of the borax solution is 0.3mol/L, the volume ratio of the borax solution to the supernatant fluid is 0.15:1, the borax contained in the added borax solution is the same as the substances of calcium nitrate contained in the calcium nitrate solution, dopamine powder is kept stirring and added, the volume ratio of the added dopamine powder to the supernatant fluid is 0.015g:1mL, and after liquid is removed by centrifugation, distilled water and absolute ethyl alcohol are used for alternately cleaning to obtain powder;
S3, dispersing the powder prepared in the step S2 in 20mL of acetone, adding ethyl titanate under stirring at a rotating speed of 300r/min for reaction for 24 hours, adding a ratio of the volume of the ethyl titanate to the volume of supernatant fluid of 0.25:1, centrifuging at a rotating speed of 2000r/min to remove liquid, drying, calcining at 600 ℃ for 0.3 hour under anaerobic condition in a tubular furnace, and then washing with dilute hydrochloric acid with pH of 1.5 to obtain a target product.
Example 3:
a method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst, in this example, using karaya wadding as a template, comprising the steps of:
S1, adding 11.0g of phoenix tree wadding, washing with distilled water and absolute ethyl alcohol to remove impurities on the surface of the phoenix tree wadding, soaking the phoenix tree wadding in Ca (OH) 2 solution with the pH of 9.5 for 15 hours, centrifuging at a high speed of 3000r/min to remove liquid, adding distilled water to adjust the pH to 8.0, and centrifuging at a low speed of 200r/min to obtain 20mL of supernatant;
s2, taking supernatant fluid obtained in the step S1, adding borax solution under stirring at a rotating speed of 240r/min, then dropwise adding calcium nitrate solution, wherein the concentration of the borax solution is 0.4mol/L, the volume ratio of the borax solution to the supernatant fluid is 0.12:1, the borax contained in the added borax solution is the same as the substances of calcium nitrate contained in the calcium nitrate solution, dopamine powder is kept stirring and added, the volume ratio of the added dopamine powder to the supernatant fluid is 0.025g:1mL, and after liquid is removed by centrifugation, distilled water and absolute ethyl alcohol are used for alternately cleaning to obtain powder;
s3, dispersing the powder prepared in the step S2 in 20mL of propanol, adding ethyl titanate under stirring at a rotating speed of 200r/min for reaction for 24 hours, adding a ratio of the volume of the ethyl titanate to the volume of the supernatant fluid of 0.3:1, centrifuging at a rotating speed of 2000r/min to remove liquid, drying, calcining at 600 ℃ for 0.45 hours under anaerobic condition in a tubular furnace, and then washing with dilute hydrochloric acid with pH of 2.0 to obtain a target product.
Example 4:
a carbon-titanium dioxide nanocomposite porous photocatalyst is prepared by the method provided in any one of embodiments 1-3, and the photocatalyst consists of an nitrogen-hybridized carbon skeleton and titanium dioxide coated outside the skeleton.
Comparative example 1:
A preparation method of a carbon-titanium dioxide nano photocatalytic material is carried out by a method provided in example 1 of Chinese patent document CN 106311196A (application number 201610578035.2).
Comparative example 2:
A method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst, which is different from example 1 in that P123 is used as a template in step S2 of this comparative example, and other technical features are the same as those of example 1.
Comparative example 3:
The preparation method of the carbon-titanium dioxide nano composite porous photocatalyst is different from the embodiment 1 in that no dopamine is added in the step S2 of the comparative example, and other technical characteristics are the same as those of the embodiment 1.
Comparative example 4:
The preparation method of the carbon-titanium dioxide nano composite porous photocatalyst is different from the embodiment 1 in that in the step S3 of the comparative example, the ratio of the volume of the added ethyl titanate to the volume of the supernatant fluid is 0.08:1, and other technical characteristics are the same as those of the embodiment 1.
Comparative example 5:
The preparation method of the carbon-titanium dioxide nano-composite porous photocatalyst is different from the embodiment 1 in that in the step S3 of the comparative example, the ratio of the volume of the added ethyl titanate to the volume of the supernatant fluid is 0.9:1, and other technical characteristics are the same as those of the embodiment 1.
Comparative example 6:
The preparation method of the carbon-titanium dioxide nano composite porous photocatalyst is different from the preparation method of the example 1 in that in the step S3 of the comparative example, the prepared product is not subjected to acid washing, and other technical characteristics are the same as those of the example 1.
Experimental example:
The photocatalysts prepared in examples 1 to 3 and comparative examples 1 to 6 were dispersed in 10mg/L of a solution containing rhodamine B dye, and a photocatalytic degradation experiment was performed using a 200 Lx-intensity xenon lamp light source for 1.5 hours, respectively, to determine the photodegradation rate of the photocatalyst to rhodamine B dye.
The experimental results are shown in the following table:
TABLE 1 photodegradation Rate of photocatalyst to rhodamine B pigment
| Group of | Photodegradation Rate (%) |
| Example 1 | 93 |
| Example 2 | 95 |
| Example 3 | 96 |
| Comparative example 1 | 80 |
| Comparative example 2 | 81 |
| Comparative example 3 | 78 |
| Comparative example 4 | 80 |
| Comparative example 5 | 83 |
| Comparative example 6 | 50 |
As shown in table 1:
example 1 has a better photodegradation rate measured in example 2 than in example 2, and the catalyst effect is better because the borate content is higher, so that the specific surface area of the photocatalyst is larger.
Example 1 showed better photodegradation than example 3, because of the higher amount of ethyl titanate as a precursor and the higher content of photocatalytic concentrated TiO 2.
The photodegradation rate measured in example 1 is superior to that measured in comparative example 1 because the method provided in comparative example 1 does not contain a carbon skeleton due to the use of aerobic sintering, and has structural defects, but the application has a better photodegradation effect by adding borate as a template and dopamine as a connecting agent, and simultaneously using anaerobic sintering during sintering, and the final product is a carbon-titanium dioxide composite structure, as shown in fig. 1, and the structure of the prepared photocatalyst is a porous structure.
In example 1, the photodegradation rate was better than that of comparative example 2, but in comparative example 2, P123 was used as a template, but it was proved by experiments that P123 did not provide a good attachment point for the linker dopamine, resulting in that although dopamine was also used as a linker, the dopamine attachment efficiency was not high, and the precursor was unable to generate TiO 2 on the dopamine surface.
In example 1, the photodegradation rate was more excellent than that in comparative example 3, and in comparative example 3, dopamine was not added as a linking agent, but although borate was used as a template, tiO 2 was directly attached to the surface of the template, and aggregation was extremely likely to occur, so that contact with a light source was not effective, resulting in lower photocatalytic efficiency.
Example 1 has a better photodegradation rate than comparative example 4, and the ratio of the volume of ethyl titanate to the volume of supernatant liquid in comparative example 4 is too low, resulting in insufficient TiO 2 content in the photocatalyst.
In example 1, the photodegradation rate measured in example 1 is superior to that measured in comparative example 5, and since the ratio of the volume of ethyl titanate to the volume of supernatant in comparative example 5 is too high, the content of TiO 2 is too high, so that the TiO 2 generated during the reaction process is agglomerated on the surface of the dopamine, and thus cannot be effectively contacted with the light source, resulting in poor photocatalytic efficiency.
In example 1, the photodegradation rate was more excellent than in comparative example 6, and since the borate as a template in the photocatalyst was not removed in comparative example 6 without acid washing, the relative content of TiO 2 in the photocatalyst per unit mass was low.
Claims (15)
1. A method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst, comprising the steps of:
s1, treating flying cotton wool, centrifuging at a high speed to remove liquid, adjusting pH, centrifuging at a low speed, and taking supernatant;
S2, taking the supernatant fluid obtained in the step S1, adding borax solution under stirring, then dropwise adding calcium nitrate solution, keeping stirring, adding dopamine powder, centrifuging to remove liquid, and then cleaning to obtain powder;
S3, dispersing the powder prepared in the step S2 in an organic solvent, adding ethyl titanate to react under stirring, centrifuging, drying, calcining without oxygen, and then pickling to obtain a target product.
2. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S1, the flying wadding is treated by soaking with alkali solution after washing.
3. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S1, the ratio of the mass of the thrown-in flying flock to the supernatant taken out is 0.2 to 0.8g:1ml.
4. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S1, the rotational speed of the high-speed centrifugation is 2000 to 4000r/min, and the rotational speed of the low-speed centrifugation is 200 to 800r/min.
5. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 4, wherein in the step S1, the rotation speed of the high-speed centrifugation is 2500 to 3500r/min, and the rotation speed of the low-speed centrifugation is 300 to 500r/min.
6. The method for preparing a carbon-titanium dioxide nano-composite porous photocatalyst according to claim 1, wherein in the step S2, the volume ratio of the borax solution to the supernatant is 0.1-0.5:1, and the borax concentration in the borax solution is 0.1-1mol/L.
7. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 6, wherein in the step S2, the volume ratio of the borax solution to the supernatant is 0.2:1, and the borax concentration in the borax solution is 0.2-0.6mol/L.
8. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S2, the borax solution is charged with the same amount of borax as the calcium nitrate solution.
9. The method for preparing a carbon-titania nanocomposite porous photocatalyst according to claim 1, wherein in the step S2, the ratio of the mass of the charged dopamine powder to the volume of the supernatant is 0.01 to 0.05 g/1 ml.
10. The method for preparing a carbon-titania nanocomposite porous photocatalyst according to claim 9, wherein in the step S2, the ratio of the mass of the charged dopamine powder to the volume of the supernatant is 0.015 to 0.03 g/1 ml.
11. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S3, a ratio of a volume of ethyl titanate charged to a volume of supernatant is 0.1 to 0.8:1.
12. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S3, a ratio of a volume of ethyl titanate charged to a volume of supernatant is 0.2 to 0.5:1.
13. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 1, wherein in the step S3, after the ethyl titanate is charged, the reaction time period is 10 to 36 hours.
14. The method for preparing a carbon-titanium dioxide nanocomposite porous photocatalyst according to claim 13, wherein in the step S3, after the ethyl titanate is charged, the reaction time period is 20 to 24 hours.
15. The carbon-titania nanocomposite porous photocatalyst prepared by the method of any one of claims 1 to 14, wherein the photocatalyst consists of an aza carbon skeleton and titania coated on the outside of the skeleton.
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