CN113877619A - Preparation method and application of carbon-nitrogen-doped titanium dioxide and biomass carbon composite material - Google Patents
Preparation method and application of carbon-nitrogen-doped titanium dioxide and biomass carbon composite material Download PDFInfo
- Publication number
- CN113877619A CN113877619A CN202111190573.1A CN202111190573A CN113877619A CN 113877619 A CN113877619 A CN 113877619A CN 202111190573 A CN202111190573 A CN 202111190573A CN 113877619 A CN113877619 A CN 113877619A
- Authority
- CN
- China
- Prior art keywords
- solution
- composite material
- carbon
- coffee grounds
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002028 Biomass Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 238000004043 dyeing Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 235000015110 jellies Nutrition 0.000 claims description 6
- 239000008274 jelly Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 13
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000007833 carbon precursor Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 235000013399 edible fruits Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 48
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 239000001045 blue dye Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a carbon-nitrogen-doped titanium dioxide and biomass carbon composite material, and the preparation method specifically comprises the following steps: crushing coffee grounds, putting the crushed coffee grounds into a dilute hydrochloric acid solution for ultrasonic treatment, washing, drying, soaking in a KOH solution, drying, calcining, washing and drying to obtain pretreated coffee grounds powder; dropwise adding tetrabutyl titanate into absolute ethyl alcohol to obtain a solution A; mixing deionized water, absolute ethyl alcohol and nitric acid to obtain a solution B; slowly dripping the solution B into the solution A, stirring, adding the pretreated coffee grounds, and stirring until fruits appearFreezing, drying and finally calcining to obtain the carbon-nitrogen doped titanium dioxide and biomass carbon composite material. Carbon-nitrogen-doped TiO is prepared by using coffee grounds as carbon precursors through a hydrothermal method and a calcination method2The organic pollutants in the printing and dyeing wastewater can be well removed through the combined action of adsorption and photocatalysis with the biomass carbon composite material.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to a preparation method of a carbon-nitrogen-doped titanium dioxide and biomass carbon composite material, and an application of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material.
Background
Water resources are one of the most important resources for human survival and development. However, as various pollutants are discharged, water pollution is increasingly serious, and the problem of water pollution also becomes a focus of attention. The organic dye is the main component of sewage, has strong stability, carcinogenicity and teratogenicity, and has great threat to ecological environment and human health.
Titanium dioxide doped with carbon and nitrogen is the most widespread TiO2One of the modification means, because the doping element affects TiO2The band gap width, the specific surface area and the active sites, thereby remarkably improving the catalytic efficiency. The introduction of carbon and nitrogen elements is beneficial to electron transfer, and the surface polarity and active sites are increased, so that the catalytic effect is enhanced. At the same time, TiO is added2The recombination with the carbon material is advantageous for suppressing the recombination of electrons and holes in the semiconductor. Therefore, the design and synthesis of carbon-nitrogen doped titanium dioxide materials for the environmental field have important significance.
The coffee grounds have a high lignocellulosic content and a porous character, and TiO2The recombination not only can provide a transfer channel for photoproduction electrons, but also can promote the quick separation of photoproduction electron holes, thereby achieving the aim of improving the photocatalytic performance.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-nitrogen-doped titanium dioxide and biomass carbon composite material, which improves the photocatalytic degradation capability of titanium dioxide on organic dye.
The invention also aims to provide application of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material as a photocatalyst in removal of organic pollutants in printing and dyeing wastewater.
The technical scheme adopted by the invention is that the preparation method of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material is implemented according to the following steps:
step 1, crushing coffee grounds, then putting the crushed coffee grounds into a dilute hydrochloric acid solution, carrying out ultrasonic treatment, washing and drying, then soaking the crushed coffee grounds into a KOH solution, and drying to obtain coffee ground powder;
step 2, placing the coffee grounds obtained in the step 1 into a tube furnace and adding the powder into the tube furnace in N2Calcining, washing and drying under the atmosphere to obtain pretreated coffee grounds;
step 3, dropwise adding tetrabutyl titanate into absolute ethyl alcohol to obtain a solution A; mixing deionized water, absolute ethyl alcohol and nitric acid to obtain a solution B;
step 4, slowly dripping the solution B obtained in the step 3 into the solution A, stirring, then adding the pretreated coffee grounds, stirring until the coffee grounds are in a jelly shape, and drying;
step 5, placing the product obtained in the step 4 into a tube furnace and adding N2Calcining in the atmosphere to obtain the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material.
The present invention is also characterized in that,
in the step 1, the concentration of the dilute hydrochloric acid solution is 0.2 mol/L; the concentration of the KOH solution is 60 g/L; the mass ratio of the KOH solution to the coffee grounds is 1: 1; the ultrasonic treatment time is 1-4h, and the soaking time is 1-4 h.
In the step 2, the calcining temperature is 1000 ℃, and the calcining time is 90 min.
In the step 3, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 5; the volume ratio of the deionized water to the absolute ethyl alcohol to the nitric acid is 3: 3: 1.
in the step 4, the stirring time for adding the solution B into the solution A is 10-30 min; stirring for 2-6h after adding the coffee powder; the drying temperature is 60-80 ℃, and the drying time is 8-10 h.
In the step 5, the calcining temperature is 450 ℃, and the calcining time is 2 h.
The other technical scheme adopted by the invention is that the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material can be applied to removal of organic pollutants in printing and dyeing wastewater.
The invention has the beneficial effects that:
the invention relates to carbon-nitrogen doped TiO2Preparation method of biomass carbon composite material, which is characterized in that coffee grounds are used as carbon precursors, and carbon-nitrogen-doped TiO is prepared by adopting hydrothermal method and calcination method2The composite material and the biomass carbon are used as a photocatalyst, and have good removal capacity on organic pollutants through the combined action of adsorption and photocatalysis; in addition, the technology has the advantages of wide raw material source, low cost and simple preparation process, and has great application potential in treating dye wastewater.
Drawings
FIG. 1 shows TiO doped with carbon and nitrogen prepared in example 2 of the present invention2A scanning electron microscope topography (I) of the biomass carbon composite material;
FIG. 2 shows carbon-nitrogen doped TiO prepared in example 2 of the present invention2A scanning electron microscope topography of the biomass carbon composite material;
FIG. 3 shows TiO doped with carbon and nitrogen prepared in example 1 of the present invention2And (3) an absorbance curve chart of the biomass carbon composite material before and after the degradation of the methylene blue dye.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The preparation method of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material is implemented according to the following steps:
step 1, crushing coffee grounds to below 200 meshes, then putting the coffee grounds into a dilute hydrochloric acid solution, carrying out ultrasonic treatment, washing and drying, then soaking the coffee grounds into a KOH solution, and drying to obtain coffee grounds powder;
the concentration of the dilute hydrochloric acid solution is 0.2 mol/L; the concentration of the KOH solution is 60 g/L;
the mass ratio of the KOH solution to the coffee grounds is 1: 1;
the ultrasonic treatment time is 1-4h, and the soaking time is 1-4 h;
step 2, placing the coffee grounds obtained in the step 1 into a tube furnace and adding the powder into the tube furnace in N2Calcining in atmosphere, washing and dryingObtaining pretreated coffee grounds powder;
the calcining temperature is 1000 ℃, and the calcining time is 90 min;
step 3, dropwise adding tetrabutyl titanate into absolute ethyl alcohol to obtain a solution A; mixing deionized water, absolute ethyl alcohol and nitric acid to obtain a solution B;
the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 5;
the volume ratio of the deionized water to the absolute ethyl alcohol to the nitric acid is 3: 3: 1;
the mass fraction of the nitric acid is 65 percent;
step 4, slowly dripping the solution B obtained in the step 3 into the solution A, stirring, then adding the pretreated coffee grounds, stirring until the coffee grounds are in a jelly shape, and drying;
stirring the solution B for 10-30min when the solution B is added into the solution A;
stirring for 2-6h after adding the coffee powder; the drying temperature is 60-80 ℃, and the drying time is 8-10 h;
step 5, placing the product obtained in the step 4 into a tube furnace and adding N2Calcining in the atmosphere to obtain a carbon-nitrogen-doped titanium dioxide and biomass carbon composite material;
the calcining temperature is 450 ℃, and the calcining time is 2 h.
The carbon-nitrogen-doped titanium dioxide and biomass carbon composite material prepared by the method can be applied to removing organic pollutants in printing and dyeing wastewater, and the specific method comprises the following steps: and mixing the composite material with a solution containing methylene blue dye, and stirring for 15-45min under illumination.
Example 1
The preparation method of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material is implemented according to the following steps:
step 1, crushing 60g of coffee grounds to below 200 meshes, soaking in 600ml of 0.2mol/L dilute hydrochloric acid solution, carrying out ultrasonic treatment for 1 hour, washing, drying, soaking in 60 g/L1L KOH solution for 1 hour, and drying;
step 2, putting the powder obtained in the step 1 into a tube furnace N2Atmosphere(s)Calcining at 1000 ℃ for 90min, washing and drying to obtain pretreated coffee grounds powder;
step 3, dripping 10ml of tetrabutyl titanate solution into 50ml of absolute ethyl alcohol solution to obtain solution A, and mixing 3ml of deionized water, 3ml of absolute ethyl alcohol and 1ml of nitric acid to obtain solution B;
step 4, slowly dripping the solution B obtained in the step 3 into the solution A, and stirring for 30 min; adding the pretreated coffee grounds into the mixed solution, stirring for 2 hours until the coffee grounds are in a jelly shape, and drying;
the drying temperature is 60 ℃, and the drying time is 8 hours;
step 5, putting the powder obtained in the step 4 into a tube furnace N2Calcining for 2h at 450 ℃ in the atmosphere to obtain carbon-nitrogen doped TiO2And biomass carbon composite material.
Example 2
The invention relates to carbon nitrogen doped TiO2The preparation method of the biomass carbon composite material is implemented according to the following steps:
step 1, 120g of coffee grounds are crushed to be below 200 meshes, soaked in 600ml of 0.2mol/L dilute hydrochloric acid solution for ultrasonic treatment for 4 hours, washed and dried. Soaking in 60 g/L2L KOH solution for 4h, and drying;
step 2, putting the powder obtained in the step 1 into a tube furnace N2Calcining for 90min at 1000 ℃ in the atmosphere, washing and drying to obtain pretreated coffee grounds powder;
step 3, dripping 10ml of tetrabutyl titanate solution into 50ml of absolute ethyl alcohol solution to obtain a solution A, and mixing 3ml of deionized water, 3ml of absolute ethyl alcohol and 1ml of nitric acid to obtain a solution B;
step 4, slowly dripping the solution B obtained in the step 3 into the solution A, and stirring for 10 min; adding the pretreated coffee grounds into the mixed solution, stirring for 6 hours until the coffee grounds are in a jelly shape, and drying;
the drying temperature is 80 ℃, and the drying time is 10 hours;
step 5, putting the powder obtained in the step 4 into a tube furnace N2Calcining for 2h at 450 ℃ in the atmosphere to obtain carbon-nitrogen doped TiO2With living beingsA carbonaceous carbon composite material.
Carbon and nitrogen doped TiO prepared in example 22Without the addition of coffee grounds, the sample had a removal of 58% of the dye methylene blue, while the sample with the addition of coffee grounds had a removal of 97% of methylene blue. The increase of the dye removal rate is due to the synergistic effect of adsorption and photocatalytic reaction, and the photocatalytic degradation capability of the composite material is enhanced.
Example 3
The invention relates to carbon nitrogen doped TiO2The preparation method of the biomass carbon composite material is implemented according to the following steps:
step 1, crushing 60g of coffee grounds to below 200 meshes, soaking in 600ml of 0.2mol/L dilute hydrochloric acid solution for ultrasonic treatment for 2 hours, washing and drying. Soaking in 60g/L of 1L KOH solution for 2h, and drying;
step 2, putting the powder obtained in the step 1 into a tube furnace N2Calcining for 90min at 1000 ℃ in the atmosphere, washing and drying to obtain pretreated coffee grounds powder;
and 3, dropwise adding 10ml of tetrabutyl titanate solution into 50ml of absolute ethanol solution to obtain a solution A. Mixing 3ml of deionized water, 3ml of absolute ethyl alcohol and 1ml of nitric acid to obtain a solution B;
step 4, slowly dripping the solution B obtained in the step 3 into the solution A, and stirring for 15 min; adding the pretreated coffee grounds into the mixed solution, stirring for 4 hours until the coffee grounds are in a jelly shape, and drying;
the drying temperature is 80 ℃, and the drying time is 9 hours;
step 5, putting the powder obtained in the step 4 into a tube furnace N2Calcining for 2h at 450 ℃ in the atmosphere to obtain carbon-nitrogen doped TiO2And biomass carbon composite material.
FIG. 1 and FIG. 2 show carbon-nitrogen-doped TiO compounds prepared in example 22According to the picture of the scanning electron microscope of the biomass carbon composite material, the surface element is in a porous structure after the coffee grounds biomass carbon is treated, and the surface is covered with a plurality of micro particles. In addition, as shown in FIG. 2, TiO is distributed on the coffee grounds2Description of TiO2The in-situ growth is realized on the coffee grounds,constructing TiO doped with carbon and nitrogen2And (3) compounding the biomass carbon with the system.
FIG. 3 shows TiO doped with hetero-carbon and nitrogen prepared in example 12And the absorbance curve of biomass carbon before and after the degradation of the methylene blue dye shows that the methylene blue is gradually degraded along with the increase of time.
The invention relates to carbon-nitrogen doped TiO2In the preparation method of the biomass carbon, the degradation mechanism of the composite material on the methylene blue dye is as follows: TiO 22The photo-generated electron-hole pairs are excited by absorbed light quanta, the electrons and the holes react with water to form hydroxyl radicals and superoxide anion radicals, and the radicals have high redox activity, so that a radical chain reaction is initiated, organic matters are degraded into small molecules, and the high-efficiency and rapid degradation of the organic matters is realized.
The carbon-nitrogen-doped TiO is prepared by taking coffee grounds as carbon precursors by adopting a hydrothermal method and a calcination method2And the biomass carbon composite material has the advantages of wide raw material source, low cost and simple preparation process, and has great application potential in treating dye wastewater.
Claims (7)
1. The preparation method of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material is characterized by comprising the following steps:
step 1, crushing coffee grounds, then putting the crushed coffee grounds into a dilute hydrochloric acid solution, carrying out ultrasonic treatment, washing and drying, then soaking the crushed coffee grounds into a KOH solution, and drying to obtain coffee ground powder;
step 2, placing the coffee grounds obtained in the step 1 into a tube furnace and adding the powder into the tube furnace in N2Calcining, washing and drying under the atmosphere to obtain pretreated coffee grounds;
step 3, dropwise adding tetrabutyl titanate into absolute ethyl alcohol to obtain a solution A; mixing deionized water, absolute ethyl alcohol and nitric acid to obtain a solution B;
step 4, slowly dripping the solution B obtained in the step 3 into the solution A, stirring, then adding the pretreated coffee grounds, stirring until the coffee grounds are in a jelly shape, and drying;
step 5, placing the product obtained in the step 4 into a tube furnace and adding N2Calcining in the atmosphere to obtain the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material.
2. The method for preparing the titanium dioxide and biomass carbon composite material doped with carbon and nitrogen according to claim 1, wherein in the step 1, the concentration of the dilute hydrochloric acid solution is 0.2 mol/L; the concentration of the KOH solution is 60 g/L; the mass ratio of the KOH solution to the coffee grounds is 1: 1; the ultrasonic treatment time is 1-4h, and the soaking time is 1-4 h.
3. The method for preparing the titanium dioxide and biomass carbon composite material doped with carbon and nitrogen according to claim 1, wherein in the step 2, the calcination temperature is 1000 ℃ and the calcination time is 90 min.
4. The method for preparing the titanium dioxide and biomass carbon composite material doped with carbon and nitrogen according to claim 1, wherein in the step 3, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1: 5; the volume ratio of the deionized water to the absolute ethyl alcohol to the nitric acid is 3: 3: 1.
5. the method for preparing the titanium dioxide and biomass carbon composite material doped with carbon and nitrogen according to claim 1, wherein in the step 4, the stirring time for adding the solution B into the solution A is 10-30 min; stirring for 2-6h after adding the coffee powder; the drying temperature is 60-80 ℃, and the drying time is 8-10 h.
6. The method for preparing the titanium dioxide and biomass carbon composite material doped with carbon and nitrogen according to claim 1, wherein in the step 5, the calcination temperature is 450 ℃ and the calcination time is 2 h.
7. The preparation method of the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material as claimed in any one of claims 1 to 6, wherein the carbon-nitrogen-doped titanium dioxide and biomass carbon composite material can be applied to the removal of organic pollutants in printing and dyeing wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111190573.1A CN113877619A (en) | 2021-10-12 | 2021-10-12 | Preparation method and application of carbon-nitrogen-doped titanium dioxide and biomass carbon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111190573.1A CN113877619A (en) | 2021-10-12 | 2021-10-12 | Preparation method and application of carbon-nitrogen-doped titanium dioxide and biomass carbon composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113877619A true CN113877619A (en) | 2022-01-04 |
Family
ID=79002484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111190573.1A Pending CN113877619A (en) | 2021-10-12 | 2021-10-12 | Preparation method and application of carbon-nitrogen-doped titanium dioxide and biomass carbon composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113877619A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818646A (en) * | 2022-12-14 | 2023-03-21 | 昆明理工大学 | Preparation method of titanium carbide powder |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465521A (en) * | 2002-07-01 | 2004-01-07 | 金车股份有限公司 | Method for making active carbon utilizing coffee bean dregs |
| CN101053845A (en) * | 2006-04-10 | 2007-10-17 | 上海市七宝中学 | Sol-gel method preparing active carbon-titanium dioxide composite photocatalyst method and application of the said photocatalyst |
| CN105032359A (en) * | 2010-03-30 | 2015-11-11 | 索尼公司 | Fungicide, photo catalytic composite material, adsorbent, and depurative |
| CN105688875A (en) * | 2016-01-11 | 2016-06-22 | 湖南大学 | TiO2-loaded biochar composite material and preparation method and application thereof |
| CN105797700A (en) * | 2016-03-17 | 2016-07-27 | 中国计量学院 | Preparation method of coconut shell activated carbon supported TiO2 photocatalyst |
| CN109985636A (en) * | 2019-03-22 | 2019-07-09 | 吕梁学院 | Preparation method based on walnut shell biomass carbon visible light catalyst |
-
2021
- 2021-10-12 CN CN202111190573.1A patent/CN113877619A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465521A (en) * | 2002-07-01 | 2004-01-07 | 金车股份有限公司 | Method for making active carbon utilizing coffee bean dregs |
| CN101053845A (en) * | 2006-04-10 | 2007-10-17 | 上海市七宝中学 | Sol-gel method preparing active carbon-titanium dioxide composite photocatalyst method and application of the said photocatalyst |
| CN105032359A (en) * | 2010-03-30 | 2015-11-11 | 索尼公司 | Fungicide, photo catalytic composite material, adsorbent, and depurative |
| CN105688875A (en) * | 2016-01-11 | 2016-06-22 | 湖南大学 | TiO2-loaded biochar composite material and preparation method and application thereof |
| CN105797700A (en) * | 2016-03-17 | 2016-07-27 | 中国计量学院 | Preparation method of coconut shell activated carbon supported TiO2 photocatalyst |
| CN109985636A (en) * | 2019-03-22 | 2019-07-09 | 吕梁学院 | Preparation method based on walnut shell biomass carbon visible light catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 肖逸帆: "纳米二氧化钛光催化剂的改性研究", 万方硕士学位论文库, 26 December 2018 (2018-12-26), pages 34 - 40 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818646A (en) * | 2022-12-14 | 2023-03-21 | 昆明理工大学 | Preparation method of titanium carbide powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108940338B (en) | Potassium-doped porous carbon nitride photocatalyst and preparation method and application thereof | |
| CN109772454B (en) | Photocatalytic film, preparation method thereof and application of photocatalytic film in degradation of disinfection byproduct precursor | |
| CN107159295B (en) | Reverse protein stone material for visible light catalytic degradation of organic pollutants and preparation method thereof | |
| CN107008467B (en) | Preparation method and application of heterojunction photocatalyst | |
| US10717120B2 (en) | Sand/water remediation method with a photocatalytic fuel cell | |
| CN110330091B (en) | Magnetic biomass functional carbon fiber based on photo-Fenton catalysis and preparation method and application thereof | |
| CN111036285B (en) | Photocatalyst of nitrogen modified perovskite composite molecular sieve and preparation method and application method thereof | |
| CN107952464B (en) | Novel photocatalytic material and double-photocatalytic-electrode self-bias pollution control system | |
| CN108067267B (en) | Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof | |
| CN113426467B (en) | Z-type boron-doped carbon nitride and silver iodide composite visible light catalyst and preparation method thereof | |
| CN109772402B (en) | Fenton-like reaction catalyst, preparation method, method for degrading organic sewage and application of Fenton-like reaction catalyst | |
| CN109126714B (en) | TiO 22/SiO2-banana peel biochar composite adsorption material and preparation method thereof | |
| CN112337490A (en) | Preparation of Mn-FeOCl material and application method of Mn-FeOCl material in catalytic degradation of malachite green in water | |
| CN112108141A (en) | Zinc oxide micron rod piezoelectric catalyst and preparation method and application thereof | |
| CN111659453B (en) | Catalyst for visible light-ozone synergistic catalysis and preparation method thereof | |
| CN111001400B (en) | Titanium dioxide material and preparation method thereof | |
| CN108654671B (en) | Composite photocatalyst and preparation method and application thereof | |
| CN109158117B (en) | Full-spectrum-response double-doped lanthanum fluoride/attapulgite up-conversion composite photocatalytic material and preparation method and application thereof | |
| CN108940349B (en) | Method for removing dye pollutants by using silver chromate/sulfur-doped nitrogen carbon Z-type photocatalyst | |
| CN111298792A (en) | Fe-doped TiO2/diatomite composite photocatalyst and preparation method and application thereof | |
| CN113877619A (en) | Preparation method and application of carbon-nitrogen-doped titanium dioxide and biomass carbon composite material | |
| CN113145158B (en) | Stripped tubular carbon nitride photocatalyst and preparation method and application thereof | |
| CN103934014B (en) | The preparation method of N doping indium sesquioxide nanometer rods/graphene oxide composite photo-catalyst | |
| CN108554427B (en) | In2O3/BiOI semiconductor composite photocatalyst and preparation method and application thereof | |
| CN111558370A (en) | Oxygen-deficient ZnO nanosheet CDs composite photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |