CN114377716A - Preparation and application of oxygen-doped carbon nitride material - Google Patents
Preparation and application of oxygen-doped carbon nitride material Download PDFInfo
- Publication number
- CN114377716A CN114377716A CN202210046068.8A CN202210046068A CN114377716A CN 114377716 A CN114377716 A CN 114377716A CN 202210046068 A CN202210046068 A CN 202210046068A CN 114377716 A CN114377716 A CN 114377716A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- bpa
- wastewater
- doped
- reaction
- 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
- 239000000463 material Substances 0.000 title claims abstract description 66
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000005070 sampling Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005286 illumination Methods 0.000 claims description 13
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 claims 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 101
- 239000000243 solution Substances 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 206010014935 Enzyme abnormality Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 bisphenol compound Chemical class 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000002611 ovarian Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 210000002307 prostate Anatomy 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
The invention discloses preparation and application of an oxygen-doped carbon nitride material, and relates to the oxygen-doped carbon nitride material, which comprises the following steps of 1, weighing 50g of urea in a crucible, covering the crucible with a cover, putting the crucible into a muffle furnace, raising the temperature to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for x hours, wherein the value of x is 2, 4 and 6; step 2, naturally cooling, taking out when the temperature is reduced to 300 ℃, and cooling to room temperature; step 3, washing and suction-filtering with 0.1mol/L HCl, washing 3 times with ultrapure water, and suction-filtering; step 4, drying in a 60 ℃ oven, cooling, grinding and sieving to obtain the oxygen-doped g-C3N4Material, denoted as oxygen doped OCNx, where x is the length of calcination. The oxygen-doped graphite carbon nitride photocatalyst is obtained by adopting a one-step calcination method, the preparation process is simple, the energy band structure of the catalyst is optimized by doping oxygen, and the photocatalytic efficiency is effectively improved.
Description
Technical Field
The invention belongs to the technical field of oxygen-doped carbon nitride materials, and particularly relates to preparation and application of an oxygen-doped carbon nitride material.
Background
The water body pollutants mainly comprise organic pollutants, heavy metals, radioactive pollutants, pathogen pollutants and the like. Among them, organic pollutants have attracted the attention of researchers due to their characteristics of easy biological accumulation and difficult degradation.
Bisphenol A (BPA) is a typical bisphenol compound (BPCs), is mainly applied to the manufacturing industries of Polycarbonate (PC), epoxy resin and the like, and is used for producing daily necessities such as baby feeding bottles, tableware, sealants and the like. The data show that the annual composite growth rate of the consumption of the epoxy resin in 2002-2013 is more than 10 percent; in 2015, the production and sale amount of epoxy resin in China accounts for more than half of the world. The wide demand and use of BPA has led to its continuous release into the environment by various means, such as: discharge of incompletely treated wastewater, leachate leakage in landfills, leaching of BPA from waste materials, and the like. The lipophilicity of BPA makes it susceptible to accumulation through the food chain into the human body, leading to high incidence of breast, ovarian, prostate, heart, diabetes and liver enzyme abnormalities. As Endocrine Disrupting Compounds (EDC), BPA release can be detrimental to animal and human health even at low exposure levels. BPA consists of two benzene rings with symmetrical structures, which determines high stability of the BPA in aqueous solution and puts higher requirements on a water treatment process.
Typical methods for removing BPA from aqueous solutions include adsorption, photocatalytic degradation, microwave catalytic degradation, ultrasonic degradation, direct oxidation, electrochemical and biochemical methods, and the like. The solar-driven photocatalytic technology is an important green technology, is clean, efficient and low in energy consumption, and has great application potential in solving global energy and environmental crisis. For contaminant removal processes that contaminate wastewater, photocatalysts are a central component. Non-metallic catalysts are of great interest because they do not produce biological toxicity due to leaching of metal ions. Wherein the graphite phase carbon nitride (g-C)3N4) As a novel semiconductor photocatalyst, the photocatalyst has the advantages of low synthesis cost, good photoresponse, proper electronic structure, high chemical stability and the like. However, the original graphite-phase carbon nitride has the defects of limited visible light absorption range, high coincidence rate of photon-generated carriers, low photocatalytic activity, low catalyst recovery rate and the like, and the application of the original graphite-phase carbon nitride in practical engineering is limited.
Various strategies such as: modification of morphology, creation of defects, doping with metal/non-metal atoms, etc. is used to increase g-C3N4The catalytic performance of (2). It has been shown that doping with oxygen can produce a local electron polarization effect, thereby promoting dissociation of excitons and carrier transport. At present, most of g-C with special nano-structure3N4The modification is carried out by a complicated and expensive process. Therefore, it is necessary to develop a catalyst which is easily available, highly active and inexpensive.
Disclosure of Invention
The invention aims to provide preparation and application of an oxygen-doped carbon nitride material aiming at the defects of the background art, the oxygen-doped graphite carbon nitride photocatalyst is obtained by adopting a one-step calcination method, the preparation process is simple, the energy band structure of the catalyst is optimized by doping oxygen, and the photocatalytic rate is effectively improved.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of an oxygen-doped carbon nitride material specifically comprises the following steps;
step 1, weighing 50g of urea in a crucible, covering the crucible with a cover, putting the crucible into a muffle furnace, raising the temperature to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for x hours, wherein the value of x is 2, 4 and 6;
step 2, naturally cooling, taking out when the temperature is reduced to 300 ℃, and cooling to room temperature;
step 3, washing and suction-filtering with 0.1mol/L HCl, washing 3 times with ultrapure water, and suction-filtering;
step 4, drying in a 60 ℃ oven, cooling, grinding and sieving to obtain the oxygen-doped g-C3N4Material, denoted as oxygen doped OCNx, where x is the length of calcination.
The application of the oxygen-doped carbon nitride material, wherein the oxygen-doped OCNx is used for removing BPA in wastewater, and the method specifically comprises the following steps;
step A, preparing 100mL of BPA solution with a specific concentration, placing the BPA solution in a 200mL conical flask, adjusting the pH value by using hydrochloric acid and sodium hydroxide solution, and adding a catalyst inwards;
step B, placing the conical flask on a magnetic stirrer with the rotating speed of 500rpm for reaction, sampling once every 20min, and taking 0.5mL each time;
step C, adding light for reaction after stirring for 60min without the optomagnetic force, wherein the light reaction lasts for 120min, and the light wavelength is more than 420 nm;
and step D, measuring the concentration of BPA in the sample by high performance liquid chromatography, specifically using a C18 chromatographic column, and setting the wavelength of an ultraviolet detector to be 278 nm.
As a further preferable scheme of the application of the oxygen-doped carbon nitride material, the oxygen-doped OCNx is used for removing BPA in wastewater, and specifically comprises the following steps;
step A1, preparing 100mL of BPA solution with the concentration of 45 mu mol/L, placing the BPA solution in a 200mL conical flask, adjusting the pH to 7.0 +/-0.1 by using hydrochloric acid and sodium hydroxide solution, and adding 0.02g of catalyst inwards;
step B1, placing the conical flask on a magnetic stirrer with the rotating speed of 500rpm for reaction, sampling once every 20min, and taking 0.5mL each time;
step C1, adding light for reaction after stirring for 60min without the optomagnetic force, wherein the light reaction lasts for 120min, and the light wavelength is more than 420 nm;
in step D1, the concentration of BPA in the sample was determined by high performance liquid chromatography, specifically using a C18 column with an ultraviolet detector wavelength of 278 nm.
As a further preferable scheme of the application of the oxygen-doped carbon nitride material, the oxygen-doped OCN6 material is used for removing BPA in wastewater, and the method specifically comprises the following steps:
step A2, preparing 100mL of BPA wastewater with the concentration of 22.5, 45 and 90 mu mol/L respectively, and adjusting the pH of the solution to 7.0 +/-0.1;
step B2, adding the prepared OCN6 material into a wastewater sample, wherein the addition amount of the material in each liter of wastewater is 0.02 g;
and step C2, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to perform reaction, sampling once every 20min, taking 0.5mL each time, and performing light reaction for 120min, wherein the light wavelength is more than 420 nm.
As a further preferable scheme of the application of the oxygen-doped carbon nitride material, the oxygen-doped OCN6 material is used for removing BPA in wastewater, and the method specifically comprises the following steps:
step A3, preparing 100mL of BPA wastewater with the concentration of 45 mu mol/L, adjusting the pH of the solution to 7.0 +/-0.1, and adding the prepared OCN6 material into a wastewater sample;
step B3, setting 4 groups of experiments, wherein 3 groups are parallel, and the addition amount of the catalyst in each group of wastewater is 0.01, 0.02, 0.03 and 0.04g respectively;
and step C3, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to perform reaction, sampling once every 20min, taking 0.5mL each time, and performing light reaction for 120min, wherein the light wavelength is more than 420 nm.
As a further preferable scheme of the application of the oxygen-doped carbon nitride material, the oxygen-doped OCN6 material is used for removing BPA in wastewater, and the method specifically comprises the following steps:
step A4, preparing 5 groups of 100mL BPA wastewater with the concentration of 45 mu mol/L, wherein each group comprises 3 groups in parallel, and adjusting the pH of the solution to 3.0 +/-0.1, 5.0 +/-0.1, 7.0 +/-0.1, 9.0 +/-0.1 and 11.0 +/-0.1;
step B4, adding the prepared OCN6 material into a wastewater sample, wherein the addition amount of the catalyst is 0.02 g;
and step C4, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to perform reaction, sampling once every 20min, taking 0.5mL each time, and performing light reaction for 120min, wherein the light wavelength is more than 420 nm.
As a further preferable scheme of the application of the oxygen-doped carbon nitride material, the oxygen-doped OCN6 material is used for removing BPA in wastewater, and the method specifically comprises the following steps:
step A5, preparing 100mL of BPA wastewater with the concentration of 45 mu mol/L, and adjusting the pH of the solution to 7.0 +/-0.1;
step B5, adding the prepared OCN6 material into a wastewater sample, wherein the addition amount of the catalyst is 0.02 g;
and step C5, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to react, sampling once every 20min, taking 0.5mL every time, keeping the light reaction for 120min, recovering the used catalyst, drying in an oven at 60 ℃ and recycling for 4 times in total, wherein the light wavelength is more than 420 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the raw materials used in the preparation process of the material are wide in source, cheap and easy to obtain;
2. the preparation process is simple and easy to control, and batch production is easy to carry out;
3. the invention constructs g-C with different oxygen contents only by adjusting the calcination time length3N4；
4. The invention can effectively improve the activity of the photocatalytic reaction.
Drawings
FIG. 1 is a schematic representation of different OCNx powders of the present invention;
FIG. 2 is a XPS spectrum of different OCNx materials of the present invention;
FIG. 3 is a graphical representation of the kinetic constants for photocatalytic degradation of BPA for different OCNx materials of the present invention;
FIG. 4 is a graphical representation of the photocatalytic degradation efficiency of OCN6 material of the present invention for BPA solutions of different concentrations;
FIG. 5 is a schematic representation of the effect of OCN6 dosing according to the invention on the photocatalytic degradation efficiency of BPA solutions;
FIG. 6 is a schematic representation of the effect of initial pH on the photocatalytic degradation of BPA by OCN6 according to the present invention;
FIG. 7 is a graphical representation of the photocatalytic degradation efficiency of OCN6 recycled in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The invention provides a simple one-step optimization method for preparing an oxygen-doped graphite carbon nitride material with adjustable and controllable oxygen, which improves the photocatalytic activity of the material and comprises the following specific steps:
weighing 50g of urea in a crucible, covering the crucible, putting the crucible into a muffle furnace, raising the temperature to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for x hours (x is 2, 4 and 6); naturally cooling, taking out when the temperature is reduced to 300 ℃, and cooling to room temperature; washing with 0.1mol/L HCl, vacuum filtering, washing with ultrapure water for 3 times, and vacuum filtering; drying in an oven at 60 ℃.
Example 1:
the oxygen-doped g-C of the invention3N4The preparation method of the catalyst comprises the following steps:
weighing 50g of urea in a crucible, covering the crucible, putting the crucible into a muffle furnace, raising the temperature to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for x hours (x is 2, 4 and 6); naturally cooling, taking out when the temperature is reduced to 300 ℃, and cooling to room temperature; washing with 0.1mol/L HCl, vacuum filtering, washing with ultrapure water for 3 times, and vacuum filtering; drying in a 60 ℃ oven, cooling, grinding and sieving to obtain the oxygen-doped g-C3N4The material, noted as OCNx, x is the length of calcination. As a comparison, undoped g-C3N4After cooling to room temperature in a muffle furnace, the sample was taken out, and the other preparation process was the same as that of OCN4 and was marked as CN.
The prepared oxygen-doped OCNx material is light yellow in appearance, the appearance of the material is shown in figure 1, and the colors are sequentially arranged from left to right from light to dark.
The obtained material was subjected to XPS characterization, and the results are shown in fig. 2:
as the calcination time period increases, the oxygen doping amount increases.
Example 2:
the oxygen-doped OCNx is used for removing BPA in wastewater, and comprises the following steps:
100mL of BPA solution with the concentration of 45 mu mol/L is prepared, the BPA solution is placed in a 200mL conical flask, the pH value is adjusted to 7.0 +/-0.1 by hydrochloric acid and sodium hydroxide solution, and 0.02g of catalyst is added inwards. A total of 4 sets of experiments (CN, OCN2, OCN4 and OCN6) were set up, with 3 replicates per set. The flask was placed on a magnetic stirrer at 500rpm for reaction, and samples were taken every 20min, 0.5mL each time. Stirring for 60min without magneto-optical force, and then adding light (wavelength > 420nm) for reaction, wherein the light reaction lasts for 120 min. The concentration of BPA in the sample was measured by high performance liquid chromatography using a C18 column with an ultraviolet detector wavelength of 278nm and a degradation efficiency as shown in FIG. 3 and Table 1. Table 1 shows the BPA removal rate from wastewater for different OCNx materials.
TABLE 1
| Photocatalyst and process for producing the same | 0 | 20 | 40 | 60 | 90 | 120 |
| CN | 3.31 | 9.24 | 9.5 | 10.72 | 12 | 12.63 |
| OCN2 | 2.81 | 6.64 | 9.04 | 0.2 | 17.89 | 36.5 |
| OCN4 | 3.68 | 14.03 | 27.44 | 41.34 | 66.27 | 92.2 |
| OCN6 | 2.74 | 23.68 | 42.22 | 65.72 | 91.12 | 100 |
The photocatalytic efficiency increases with increasing oxygen content, with OCN6 being the most catalytically active.
Example 3:
the OCN6 material of the invention is used for removing BPA in wastewater, and comprises the following steps:
100mL of BPA wastewater with the concentration of 22.5, 45 and 90 mu mol/L are respectively prepared by 3 parts, the pH of the solution is adjusted to be 7.0 +/-0.1, the OCN6 material prepared in example 1 is added into a wastewater sample, the addition amount of the OCN6 material in each liter of wastewater is 0.02g, a reactor is placed on a magnetic stirrer with the rotating speed of 500rpm, illumination (> 420nm) is applied for reaction, the sampling is carried out once every 20min, 0.5mL is taken each time, and the illumination reaction lasts for 120 min. The concentration of BPA in the sample was measured by high performance liquid chromatography using a C18 column, an ultraviolet detector wavelength of 278nm, and a degradation efficiency as shown in FIG. 4.
As can be seen in fig. 4, the BPA removal rate of OCN6 material decreased with increasing initial concentration of BPA.
Example 4:
the OCN6 material of the invention is used for removing BPA in wastewater, and comprises the following steps:
100mL of BPA wastewater with a concentration of 45. mu. mol/L was prepared, the pH of the solution was adjusted to 7.0. + -. 0.1, and OCN6 material prepared in example 1 was added to a wastewater sample. Setting 4 groups of experiments (3 parallel in each group), wherein the addition amount of the catalyst in each group of wastewater is respectively 0.01, 0.02, 0.03 and 0.04g, placing the reactor on a magnetic stirrer with the rotating speed of 500rpm, applying illumination (more than 420nm) to carry out reaction, sampling once every 20min, taking 0.5mL each time, and keeping the illumination reaction for 120 min. The concentration of BPA in the sample was measured by high performance liquid chromatography using a C18 column, an ultraviolet detector wavelength of 278nm, and a degradation efficiency as shown in FIG. 5.
As can be seen from FIG. 5, the removal rate of BPA by OCN6 material increased with increasing catalyst dosage, and more catalyst provided more adsorption sites and more reactive sites.
Example 5:
the OCN6 material of the invention is used for removing BPA in wastewater, and comprises the following steps:
100mL of 5 sets of BPA wastewater having a concentration of 45. mu. mol/L were prepared, 3 of each set were in parallel, the pH of the solution was adjusted to 3.0. + -. 0.1, 5.0. + -. 0.1, 7.0. + -. 0.1, 9.0. + -. 0.1 and 11.0. + -. 0.1, and the OCN6 material prepared in example 1 was added to the wastewater sample in an amount of 0.02g of the catalyst. The reactor is placed on a magnetic stirrer with the rotating speed of 500rpm, illumination (more than 420nm) is applied to carry out reaction, the sampling is carried out once every 20min, 0.5mL is taken each time, and the illumination reaction lasts for 120 min. The concentration of BPA in the sample was measured by high performance liquid chromatography using a C18 column, an ultraviolet detector wavelength of 278nm, and a degradation efficiency as shown in FIG. 6.
As can be seen in FIG. 6, the removal rate of BPA by OCN6 material decreased with increasing initial pH of the solution.
Example 6:
the OCN6 material of the invention is used for removing BPA in wastewater, and comprises the following steps:
100mL of BPA wastewater with a concentration of 45. mu. mol/L was prepared, the pH of the solution was adjusted to 7.0. + -. 0.1, and OCN6 material prepared in example 1 was added to a wastewater sample in an amount of 0.02g of catalyst. The reactor is placed on a magnetic stirrer with the rotating speed of 500rpm, illumination (more than 420nm) is applied to carry out reaction, the sampling is carried out once every 20min, 0.5mL is taken each time, and the illumination reaction lasts for 120 min. The used catalyst is recovered and dried in a 60 ℃ oven for recycling, and the cycle is 4 times. The concentration of BPA in the sample was measured by high performance liquid chromatography using a C18 column, an ultraviolet detector wavelength of 278nm, and a degradation efficiency as shown in FIG. 7.
As can be seen from FIG. 7, after 4 cycles, the removal efficiency of OCN6 material to BPA at 120min still remained high, and the removal rate of BPA was above 96%.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The preparation method of the oxygen-doped carbon nitride material is characterized by comprising the following steps of;
step 1, weighing 50g of urea in a crucible, covering the crucible with a cover, putting the crucible into a muffle furnace, raising the temperature to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for x hours, wherein the value of x is 2, 4 and 6;
step 2, naturally cooling, taking out when the temperature is reduced to 300 ℃, and cooling to room temperature;
step 3, washing and suction-filtering with 0.1mol/L HCl, washing 3 times with ultrapure water, and suction-filtering;
step 4, drying in a 60 ℃ oven, cooling, grinding and sieving to obtain the oxygen-doped g-C3N4Material, denoted as oxygen doped OCNx, where x is the length of calcination.
2. The use of the oxygen-doped carbon nitride material according to claim 1, wherein the oxygen-doped OCNx is used for removing BPA in wastewater, and comprises the following steps;
step A, preparing 100mL of BPA solution with a specific concentration, placing the BPA solution in a 200mL conical flask, adjusting the pH value by using hydrochloric acid and sodium hydroxide solution, and adding a catalyst inwards;
step B, placing the conical flask on a magnetic stirrer with the rotating speed of 500rpm for reaction, sampling once every 20min, and taking 0.5mL each time;
step C, adding xenon lamp illumination for reaction after stirring for 60min without the optical magnetic force, wherein the illumination reaction lasts for 120min, and the illumination wavelength is more than 420 nm;
and step D, measuring the concentration of BPA in the sample by high performance liquid chromatography, specifically using a C18 chromatographic column, and setting the wavelength of an ultraviolet detector to be 278 nm.
3. The use of the oxygen-doped carbon nitride material according to claim 2, wherein the oxygen-doped OCNx is used for removing BPA in wastewater, and comprises the following steps;
step A1, preparing 100mL of BPA solution with the concentration of 45 mu mol/L, placing the BPA solution in a 200mL conical flask, adjusting the pH to 7.0 +/-0.1 by using hydrochloric acid and sodium hydroxide solution, and adding 0.02g of catalyst inwards;
step B1, placing the conical flask on a magnetic stirrer with the rotating speed of 500rpm for reaction, sampling once every 20min, and taking 0.5mL each time;
step C1, adding light for reaction after stirring for 60min without the optomagnetic force, wherein the light reaction lasts for 120min, and the light wavelength is more than 420 nm;
in step D1, the concentration of BPA in the sample was determined by high performance liquid chromatography, specifically using a C18 column with an ultraviolet detector wavelength of 278 nm.
4. The use of the oxygen-doped carbon nitride material according to claim 2, wherein the oxygen-doped OCN6 material is used for removing BPA in wastewater, and comprises the following steps:
step A2, preparing 100mL of BPA wastewater with the concentration of 22.5, 45 and 90 mu mol/L respectively, and adjusting the pH of the solution to 7.0 +/-0.1;
step B2, adding the prepared 0CN6 material into a wastewater sample, wherein the addition amount of the material in each liter of wastewater is 0.02 g;
and step C2, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to perform reaction, sampling once every 20min, taking 0.5mL each time, and performing light reaction for 120min, wherein the light wavelength is more than 420 nm.
5. The use of the oxygen-doped carbon nitride material according to claim 2, wherein the oxygen-doped 0CN6 material is used for removing BPA in wastewater, and comprises the following steps:
step A3, preparing 100mL of BPA wastewater with the concentration of 45 mu mol/L, adjusting the pH of the solution to 7.0 +/-0.1, and adding the prepared OCN6 material into a wastewater sample;
step B3, setting 4 groups of experiments, wherein 3 groups are parallel, and the addition amount of the catalyst in each group of wastewater is 0.01, 0.02, 0.03 and 0.04g respectively;
and step C3, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to perform reaction, sampling once every 20min, taking 0.5mL each time, and performing light reaction for 120min, wherein the light wavelength is more than 420 nm.
6. The use of the oxygen-doped carbon nitride material according to claim 2, wherein the oxygen-doped OCN6 material is used for removing BPA in wastewater, and comprises the following steps:
step A4, preparing 5 groups of 100mL BPA wastewater with the concentration of 45 mu mol/L, wherein each group comprises 3 groups in parallel, and adjusting the pH of the solution to 3.0 +/-0.1, 5.0 +/-0.1, 7.0 +/-0.1, 9.0 +/-0.1 and 11.0 +/-0.1;
step B4, adding the prepared OCN6 material into a wastewater sample, wherein the addition amount of the catalyst is 0.02 g;
and step C4, placing the reactor on a magnetic stirrer with the rotation speed of 500rpm, applying light to perform reaction, sampling once every 20min, taking 0.5mL each time, and performing light reaction for 120min, wherein the light wavelength is more than 420 nm.
7. The use of the oxygen-doped carbon nitride material according to claim 2, wherein the oxygen-doped 0CN6 material is used for removing BPA in wastewater, and comprises the following steps:
step A5, preparing 100mL of BPA wastewater with the concentration of 45 mu mol/L, and adjusting the pH of the solution to 7.0 +/-0.1;
step B5, adding the prepared OCN6 material into a wastewater sample, wherein the addition amount of the catalyst is 0.02 g;
and step C5, placing the reactor on a magnetic stirrer with the rotating speed of 500rpm, applying illumination with the wavelength of more than 420nm for reaction, sampling once every 20min, taking 0.5mL each time, continuing the illumination reaction for 120min, recovering the used catalyst, drying in an oven at 60 ℃ and recycling, and recycling for 4 times in total.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210046068.8A CN114377716A (en) | 2022-01-14 | 2022-01-14 | Preparation and application of oxygen-doped carbon nitride material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210046068.8A CN114377716A (en) | 2022-01-14 | 2022-01-14 | Preparation and application of oxygen-doped carbon nitride material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114377716A true CN114377716A (en) | 2022-04-22 |
Family
ID=81202380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210046068.8A Pending CN114377716A (en) | 2022-01-14 | 2022-01-14 | Preparation and application of oxygen-doped carbon nitride material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114377716A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115999606A (en) * | 2022-12-19 | 2023-04-25 | 广东工业大学 | Oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669760A (en) * | 2016-12-28 | 2017-05-17 | 广州中国科学院沈阳自动化研究所分所 | Sulfur-doped carbon nitride photocatalyst as well as preparation method and application thereof |
| CN107649168A (en) * | 2017-11-09 | 2018-02-02 | 江苏省环境科学研究院 | The method of bisphenol-A and its catalyst used in a kind of photocatalytic degradation water |
| CN108499590A (en) * | 2018-03-28 | 2018-09-07 | 华北电力大学 | A kind of oxygen doping nitride porous carbon visible light catalytic material and preparation method thereof |
| CN108686692A (en) * | 2018-03-30 | 2018-10-23 | 广东工业大学 | A kind of photochemical catalyst and its preparation method and application of oxygen doping carbonitride |
| CN109647481A (en) * | 2019-01-07 | 2019-04-19 | 广州大学 | The preparation of oxygen doping graphite phase carbon nitride and its application in catalytic activation persulfate degradation water pollutant |
| CN110342477A (en) * | 2019-06-10 | 2019-10-18 | 西安理工大学 | A kind of oxygen doping nitride porous carbon nanosheet and preparation method thereof |
| CN110433851A (en) * | 2019-09-04 | 2019-11-12 | 广州大学 | A kind of honeycomb oxygen doping carbon nitride photocatalyst and its preparation method and application |
| CN111729683A (en) * | 2020-07-14 | 2020-10-02 | 广东石油化工学院 | Oxygen-doped graphite-like phase carbon nitride photocatalyst and preparation method and application thereof |
| CN111889130A (en) * | 2020-07-30 | 2020-11-06 | 大连工业大学 | Preparation of modified carbon nitride photocatalyst and application of modified carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of glucose |
| CN112121854A (en) * | 2020-09-29 | 2020-12-25 | 江南大学 | Self-assembled tetra (4-carboxyphenyl) porphyrin/oxygen-doped carbon nitride nanosheet heterojunction photocatalyst and preparation method and application thereof |
-
2022
- 2022-01-14 CN CN202210046068.8A patent/CN114377716A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669760A (en) * | 2016-12-28 | 2017-05-17 | 广州中国科学院沈阳自动化研究所分所 | Sulfur-doped carbon nitride photocatalyst as well as preparation method and application thereof |
| CN107649168A (en) * | 2017-11-09 | 2018-02-02 | 江苏省环境科学研究院 | The method of bisphenol-A and its catalyst used in a kind of photocatalytic degradation water |
| CN108499590A (en) * | 2018-03-28 | 2018-09-07 | 华北电力大学 | A kind of oxygen doping nitride porous carbon visible light catalytic material and preparation method thereof |
| CN108686692A (en) * | 2018-03-30 | 2018-10-23 | 广东工业大学 | A kind of photochemical catalyst and its preparation method and application of oxygen doping carbonitride |
| CN109647481A (en) * | 2019-01-07 | 2019-04-19 | 广州大学 | The preparation of oxygen doping graphite phase carbon nitride and its application in catalytic activation persulfate degradation water pollutant |
| CN110342477A (en) * | 2019-06-10 | 2019-10-18 | 西安理工大学 | A kind of oxygen doping nitride porous carbon nanosheet and preparation method thereof |
| CN110433851A (en) * | 2019-09-04 | 2019-11-12 | 广州大学 | A kind of honeycomb oxygen doping carbon nitride photocatalyst and its preparation method and application |
| CN111729683A (en) * | 2020-07-14 | 2020-10-02 | 广东石油化工学院 | Oxygen-doped graphite-like phase carbon nitride photocatalyst and preparation method and application thereof |
| CN111889130A (en) * | 2020-07-30 | 2020-11-06 | 大连工业大学 | Preparation of modified carbon nitride photocatalyst and application of modified carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of glucose |
| CN112121854A (en) * | 2020-09-29 | 2020-12-25 | 江南大学 | Self-assembled tetra (4-carboxyphenyl) porphyrin/oxygen-doped carbon nitride nanosheet heterojunction photocatalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| QINGWEN TANG ET AL.: "One-step exfoliation of polymeric C3N4 by atmospheric oxygen doping for photocatalytic persulfate activation", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 579, pages 455 - 462, XP086268716, DOI: 10.1016/j.jcis.2020.06.064 * |
| RONG TANG ET AL.: "Preparation of oxygen doped graphitic carbon nitride and its visible-light photocatalytic performance on biphenol A degradation", WATER SCIENCE & TECHNOLOGY, pages 1 - 11 * |
| 王燚凡 等: "超薄硫掺杂石墨相氮化碳纳米片光催化降解双酚A", 环境科学研究, vol. 34, no. 12, pages 2859 - 2866 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115999606A (en) * | 2022-12-19 | 2023-04-25 | 广东工业大学 | Oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107649168B (en) | Method for degrading bisphenol A in water through photocatalysis and catalyst used by method | |
| CN102580742A (en) | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof | |
| CN106669744B (en) | Ag2Mo2O7@ AgBr composite photocatalyst and preparation method thereof | |
| CN110064408B (en) | Preparation method of iron sulfide-loaded alpha crystal form iron oxyhydroxide catalyst | |
| CN107626335A (en) | A kind of bismuth system/carbonitride composite catalyst and its preparation method and application | |
| CN103191766A (en) | CdS/g-C3N4 composite visible light catalyst, preparation method and application | |
| CN109806900B (en) | Molecular imprinting type Ag/Ag3VO4Preparation method and application of/CN nanosheet composite photocatalyst | |
| CN109529814B (en) | Visible light driven inverse proteolith photocatalytic material, preparation method thereof and degradation removal of organic pollutants in water body by using visible light driven inverse proteolith photocatalytic material | |
| CN108246334A (en) | A kind of functionalization tri compound catalysis material and preparation method thereof and purposes | |
| CN110756163A (en) | Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof | |
| CN113731448A (en) | Homogeneous Fenton cocatalyst, and preparation method and application thereof | |
| CN114377716A (en) | Preparation and application of oxygen-doped carbon nitride material | |
| CN111410237B (en) | Method for recycling waste polluted biomass | |
| CN103721713A (en) | Three-phase composite visible-light-driven photocatalyst capable of efficiently degrading dyes | |
| CN111359676B (en) | MOF-based composite material and preparation method and application thereof | |
| CN103212405B (en) | Cadmium-doped bismuth molybdate visible-light-induced photocatalyst and preparation method and application of cadmium-doped bismuth molybdate visible-light-induced photocatalyst | |
| CN111346675B (en) | Preparation method and application of acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst | |
| CN112495400A (en) | SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI) | |
| CN108144585B (en) | Ternary magnetic composite material for heavy metal and dye wastewater treatment and preparation method thereof | |
| CN107029725B (en) | Carbon quantum dot-nickel titanate compound degradation agent and preparation method thereof of degradation antibiotic | |
| CN110354868A (en) | A kind of preparation method of magnetic composite microsphere load doped yttrium photochemical catalyst | |
| CN108714428A (en) | A kind of nano wire photochemical catalyst and the preparation method and application thereof | |
| CN107224987A (en) | CdSe quantum dot is embedded in culm charcoal and Bi12TiO20The preparation and its application of composite photo-catalyst | |
| Sun et al. | Electron beam irradiation treatment of Ag/Bi 2 WO 6/CdWO 4 heterogeneous material with enhanced photocatalytic activity | |
| CN111533360A (en) | Treatment method of chromium-containing wastewater |
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 |