CN113649044A - Nitrogen-sulfur double-doped porous carbon material catalyst and preparation method thereof - Google Patents

Nitrogen-sulfur double-doped porous carbon material catalyst and preparation method thereof Download PDF

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CN113649044A
CN113649044A CN202110944217.8A CN202110944217A CN113649044A CN 113649044 A CN113649044 A CN 113649044A CN 202110944217 A CN202110944217 A CN 202110944217A CN 113649044 A CN113649044 A CN 113649044A
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nitrogen
sulfur
carbon material
porous carbon
temperature
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刘仁兰
安宁
赵敏
郑向勇
刘隽
黄先锋
贝克
金展
王奇
李军
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Wenzhou University
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    • 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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
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Abstract

The invention discloses a nitrogen-sulfur double-doped porous carbon material catalyst and a preparation method thereof, and relates to the technical field of carbon catalytic preparation. According to the nitrogen-sulfur double-doped porous carbon material catalyst and the preparation method thereof, the porous carbon material comprises a nitrogen-sulfur source and a carbon source which are 1-50% in mass ratio, the carbon source is glucose, the nitrogen-sulfur source is cysteine, and the nonmetal nitrogen-sulfur double-doped porous carbon material is prepared by a hydrothermal method and a high-temperature alkali activation method, wherein nitrogen and sulfur co-doping ensures the catalytic stability of the catalyst, and the synergistic effect between the nitrogen and sulfur promotes the adsorption and catalytic degradation of antibiotic organic pollutants, so that the catalyst has better catalytic performance than a single-element doped carbon material. The raw materials required for preparing the catalyst are green and pollution-free, are easy to purchase, have low cost and simple preparation process, are easy for large-scale production, and can be used in the fields of treatment of organic polluted water bodies in the environment, deep purification treatment of drinking water and the like.

Description

Nitrogen-sulfur double-doped porous carbon material catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of carbon catalytic preparation, in particular to a nitrogen-sulfur double-doped porous carbon material catalyst and a preparation method thereof.
Background
The medicines and personal care products (PPCPs for short) mainly comprise medicines (antibiotics, hormones and the like) and personal care products (antibacterial agents, disinfectants, antiseptics and the like). Most PPCPs have water solubility and complex structure, can inhibit or influence the functions of organisms at low concentration, and belong to persistent refractory organic matters. As PPCPs belong to refractory organic matters, the PPCPs are difficult to completely remove by using the traditional physical method (such as adsorption, sedimentation and the like) and biological method (such as activated sludge method), and the PPCPs exist in the environment for a long time, which not only can cause the reduction of microbial diversity, but also can bring certain ecological risks to human health and other animals and plants. Therefore, the PPCPs pollution problem has become an important global concern.
The persulfate is activated by preparing the non-metal doped carbon catalyst, the general activation process is that transition metal is loaded on an inorganic carrier by a high-temperature roasting method, the carbon-based supported catalyst has higher activity, and is often used as an inorganic carrier due to large specific surface area of activated carbon and biochar and easy loading of other molecules; meanwhile, the carbon-based material has rich pore structures and more oxygen-containing functional groups on the surface, so that the carbon-based material can adsorb organic pollutants and degrade the pollutants by activating persulfate, and if the carbon-based material is modified to a certain degree, for example, nitrogen can be doped in, the catalytic capacity of the carbon-based material can be greatly improved. The carbon material can be used as an inorganic catalyst capable of replacing transition metal oxides, is an environment-friendly material, such as activated carbon, carbon nanotubes, nanodiamonds, graphene, ordered mesoporous carbon, some doped carbon materials and the like, has small changes in oxygen-containing functional groups and structures on the surface of the carbon material after a catalyst activator or pollutants are adsorbed, shows excellent stability, can be repeatedly used, but may be relatively high in cost. The activation of the persulfate by the carbon-based material is mainly completed through electron transfer between the carbon-based material and the persulfate, and the oxidation-reduction potential plays an important role in the process, and is certainly influenced by factors such as the structure and the composition of the carbon material.
In this regard, Li et al have passed through various activators (ZnCl)2、KOH、CO2) Nitrogen and sulfur co-doped Graphene (N, S-G) is prepared and used for activating persulfate to degrade phenol, and N, S-G prepared by KOH activation shows excellent performance, and the activation energy of the N, S-G is 24.65kJ/mol (Li X, Wang J, Duan X, et al, Fine-Tuning/non-radial Pathway on Graphene by ports Engineering and Doping stratages [ J]ACS Catalysis,2021: 4848-4861). Ding et al prepared single doped (NBC, SBC) and double doped (NSBC) carbon materials from straw as precursor for adsorption and catalytic degradation of metolachlor, while NSBC has no optimal performance and has a specific surface area of only 109.2m2/g(Dahu Ding,Shengjiong Yang,Xiaoyong Qian,Liwei Chen,Tianming Cai.Nitrogen-doping positively whilst sulfur-doping negatively affect the catalytic activity of biochar for the degradation of organic contaminant[J].Applied Catalysis B:Environmental,2020,263)。
For another example, Chinese patent CN110415992A discloses a peach gum, KOH and thiourea obtained by dissolving in waterThe catalyst mainly applied to the electrochemical field is obtained by reaction precursor, freeze-drying, high-temperature calcination and acid washing. Chinese patent CN106207204A discloses a catalyst N-S-C prepared by using marine polysaccharide sodium alginate as a carbon source and thiourea as a nitrogen-sulfur source and calcining at high temperature in an inert atmosphere, wherein the surface of the catalyst N-S-C presents holes with the size of about 100-400 nm, and the specific surface area is 153.6-181.3 m2(ii) in terms of/g. However, the low doping amount and the small specific surface area of the catalyst restrict the further improvement of the performance of the porous carbon material. Therefore, the preparation of the nitrogen-sulfur double-doped porous carbon material catalyst with large specific surface area and high catalytic performance by adopting a simple synthesis method becomes an important research direction.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the problems of low doping amount, small specific surface area of the catalyst and the like in the preparation method of the carbon catalyst in the prior art, the invention provides a nitrogen-sulfur double-doped porous carbon material catalyst and a preparation method thereof.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a nitrogen-sulfur double-doped porous carbon material catalyst comprises a nitrogen-sulfur source and a carbon source which are 1-50% in mass ratio, wherein the carbon source is glucose, the nitrogen-sulfur source is cysteine, the raw material is green and pollution-free, easy to purchase and low in cost, and the nitrogen-sulfur double-doped porous carbon material can be used for water purification, air purification, chemical catalysis or energy storage; the specific surface area of the nitrogen-sulfur double-doped porous carbon material is 1000-2000 m2The catalyst provides rich active sites for the adsorption and degradation of the biological organic pollutants, and is beneficial to improving the catalytic activity of the catalyst. The co-doping of nitrogen and sulfur not only ensures the catalytic stability of the catalyst, but also ensures the catalytic stability of the catalystThe synergistic effect promotes the adsorption and catalytic degradation of antibiotic organic pollutants, and the catalytic performance is better than that of a single element doped carbon material.
In a further technical scheme, the mass ratio of the nitrogen-sulfur source to the carbon source is 5-40%.
According to the further technical scheme, the nitrogen and sulfur elements are uniformly distributed on the surface of the porous carbon material, the aperture of the porous carbon material is 2-50nm, the nitrogen-sulfur double-doped porous carbon material is in a black powder shape, and compared with an undoped porous carbon material (with a large hole and the aperture of 122nm), the nitrogen-sulfur double-doped porous carbon material has a richer hole structure and provides more adsorption and reaction active sites and electron migration channels for adsorption and degradation of organic matters such as antibiotics, so that the degradation efficiency of the organic matters such as antibiotics is improved.
A preparation method of a nitrogen-sulfur double-doped porous carbon material catalyst comprises the following steps:
the method comprises the following steps: weighing a certain amount of carbon source, nitrogen source and sulfur source, mixing and dispersing in an aqueous solution, transferring to a hydrothermal reaction kettle container, heating to a certain temperature and keeping for a certain time to obtain a carbon material containing carbon, nitrogen and sulfur;
step two, putting the synthesized carbon material containing carbon, nitrogen and sulfur into a quartz glass container, introducing inert gas as protective gas, calcining at high temperature for a certain time, naturally cooling, grinding and crushing to obtain a nitrogen-sulfur double-doped carbonized material;
and step three, putting the synthesized nitrogen-sulfur double-doped carbonized material into a customized crucible, sequentially adding a sodium hydroxide solution and absolute ethyl alcohol in a certain proportion, uniformly stirring, transferring into an oven to be dried at a certain temperature, transferring into a high-temperature tubular furnace, introducing inert gas as protective gas, calcining at a high temperature for a certain time, and naturally cooling to obtain the nitrogen-sulfur double-doped porous carbon material catalyst.
In the step one, the nitrogen source is selected from one, two or more of urea, melamine and L-cysteine; the sulfur source is selected from one, two or more of sodium sulfide, thiourea and L-cysteine; the carbon source is selected from one, two or more of glucose, graphene oxide and cyclodextrin.
According to a further technical scheme, in the first step, the temperature in the hydrothermal reaction kettle container is 160-200 ℃, and preferably 160-180 ℃; the reaction time is 8-15 hours, preferably 10-12 hours, and after the hydrothermal reaction is finished, the sample is ground.
In the second step, the temperature is raised to 200-500 ℃ at the rate of 1-8 ℃/min in the high-temperature calcination process, and the temperature is maintained for 0.5-2.0 hours.
In the third step, the ratio of the nitrogen-sulfur double-doped carbonized material, 1mol/L sodium hydroxide and absolute ethyl alcohol is (0.05 g-0.2 g): (1 mL-4 mL): (0.2 mL-0.8 mL), preferably (0.11g): 2 mL: 0.4 mL.
In the third step, the high-temperature calcination process is heated to 700-1000 ℃ at the speed of 1-8 ℃/min, the temperature is kept for 1.0-2.0 hours, then the temperature is reduced to 400-500 ℃ at the speed of 10-15 ℃/min, and finally the product is naturally cooled to room temperature.
According to a further technical scheme, in the second step and the third step, the inert protective gas is high-purity nitrogen and argon, and the purity is more than or equal to 99.99%.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) according to the nitrogen-sulfur double-doped porous carbon material catalyst and the preparation method thereof, glucose is added as a carbon source, cysteine is used as a nitrogen source and a sulfur source, and a one-step hydrothermal method, one-time high-temperature pyrolysis carbonization and one-time high-temperature alkali activation are utilized to prepare the nitrogen-sulfur double-doped porous carbon material, wherein the specific surface area of the nitrogen-sulfur double-doped porous carbon material is 1000-2000 m2The catalyst provides rich active sites for the adsorption and degradation of biological organic pollutants, and is beneficial to improving the catalytic activity of the catalyst; the preparation raw materials of the catalyst are green and pollution-free, are easy to purchase, have low cost and simple preparation process, are easy for large-scale production, and the nitrogen-sulfur double-doped porous carbon material can be used for water purification and air purificationChemical catalysis or energy storage;
(2) according to the nitrogen-sulfur double-doped porous carbon material catalyst and the preparation method thereof, nitrogen and sulfur elements are uniformly distributed on the surface of a porous carbon material, the aperture of the porous carbon material is 2-50nm, compared with an undoped porous carbon material, the nitrogen-sulfur double-doped porous carbon material has a richer pore structure, and provides more adsorption and reaction active sites and electron migration channels for adsorption and degradation of organic matters such as antibiotics, so that the degradation efficiency of the organic matters such as antibiotics is improved;
(3) according to the nitrogen-sulfur double-doped porous carbon material catalyst and the preparation method thereof, nitrogen elements in the porous carbon material are covalently bonded with carbon in the porous carbon material through pyrrole nitrogen, pyridine nitrogen and graphite nitrogen, and sulfur elements are covalently bonded with carbon in the porous carbon material through thiophene sulfur (C-S-C) and sulfur oxide (C-SOX-C). The co-doping of nitrogen and sulfur not only ensures the catalytic stability of the catalyst, but also promotes the adsorption and catalytic degradation of antibiotic organic pollutants under the synergistic effect of the nitrogen and sulfur, and has better catalytic performance than a single element-doped carbon material.
Drawings
FIG. 1(a) is a scanning electron micrograph of N, S-CSs 900-10% -OH obtained in example B, (B) is N, S-CSs-10% obtained in comparative example D, and (c) is CSs900-OH obtained in comparative example A.
FIG. 2 shows the full X-ray photoelectron spectroscopy spectra of example A, B, C, D and comparative example A, B, C.
FIG. 3(a) is example B, (B) is comparative example D, and (c) is N of comparative example A2Adsorption and desorption curves.
FIG. 4(a) shows the ratio of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen in example A, example B, example C and example D, and (B) shows the ratio of thiophene sulfur and sulfur oxide.
FIG. 5(a) is the kinetics of catalytic degradation of oxytetracycline of example B, and (B) is the kinetics of degradation of oxytetracycline of comparative example A, B, C, D.
FIG. 6 is a schematic diagram of the reaction activation energy of example B.
FIG. 7(a) shows the free radical quenching experiment of example B for terramycin degradation, (B) shows the electron paramagnetic resonance spectrum of superoxide radical in example B for terramycin degradation, (c) shows the electron paramagnetic resonance spectrum of sulfate radical and hydroxyl radical in example B for terramycin degradation, and (d) shows the electron paramagnetic resonance spectrum of singlet oxygen in example B for terramycin degradation.
FIG. 8 is a recycle experiment of catalytic degradation of oxytetracycline for example B, comparative example A and comparative example B.
FIG. 9 is a SEM image of example B after five recycles.
FIG. 10 is a Fourier transform infrared spectrum of example B after five recycles.
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.
Example 1
The porous carbon material catalyst doped with nitrogen and sulfur double-doped with porous carbon material comprises a nitrogen and sulfur source and a carbon source which are 1-50% in mass ratio, wherein the carbon source is glucose, and the nitrogen and sulfur source is cysteine, so that the raw material is green and pollution-free, is easy to purchase, and is low in cost; the specific surface area of the nitrogen-sulfur double-doped porous carbon material is 1000-2000 m2The catalyst provides rich active sites for the adsorption and degradation of biological organic pollutants, and is beneficial to improving the catalytic activity of the catalyst; nitrogen is covalently bonded to carbon in the porous carbon material through pyrrole nitrogen, pyridine nitrogen and graphite nitrogen, and sulfur is covalently bonded to carbon in the porous carbon material through thiophene sulfur (C-S-C) and sulfur oxide (C-SOX-C). The co-doping of nitrogen and sulfur not only ensures the catalytic stability of the catalyst, but also promotes the adsorption and catalytic degradation of antibiotic organic pollutants under the synergistic effect of the nitrogen and sulfur, and has better catalytic performance than a single element-doped carbon material. The catalyst can be used in the fields of water purification, air purification, chemical catalysis or energy storage and the like.
In a further technical scheme, the mass ratio of the nitrogen-sulfur source to the carbon source is 5-40%, as shown in table 1.
TABLE 1 degradation rates of different types of carbon materials for oxytetracycline, sulfamethoxazole, parachlorophenol and bisphenol A
Figure BDA0003216061760000051
Example 2
The basic structure of the nitrogen-sulfur double-doped porous carbon material catalyst of the embodiment is the same as that of the embodiment 1, and the differences and the improvements are as follows: the nitrogen and sulfur elements are uniformly distributed on the surface of the porous carbon material, the aperture of the porous carbon material is 2-50nm, the nitrogen-sulfur double-doped porous carbon material is in a black powder shape, and compared with an undoped porous carbon material (with a large hole and the aperture of 122nm), the nitrogen-sulfur double-doped porous carbon material has a richer hole structure, provides more adsorption and reaction active sites and electron migration channels for adsorption degradation of organic matters such as antibiotics, and accordingly improves the degradation efficiency of the organic matters such as antibiotics.
Example 3
The basic structure of the preparation method of the nitrogen-sulfur double-doped porous carbon material catalyst of the embodiment is the same as that of the embodiment 2, and the differences and improvements are as follows: the method comprises the following steps:
the method comprises the following steps: weighing a certain amount of carbon source, nitrogen source and sulfur source, mixing and dispersing in an aqueous solution, transferring to a hydrothermal reaction kettle container, heating to a certain temperature and keeping for a certain time to obtain a carbon material containing carbon, nitrogen and sulfur;
step two, putting the synthesized carbon material containing carbon, nitrogen and sulfur into a quartz glass container, introducing inert gas as protective gas, calcining at high temperature for a certain time, naturally cooling, grinding and crushing to obtain a nitrogen-sulfur double-doped carbonized material;
and step three, putting the synthesized nitrogen-sulfur double-doped carbonized material into a customized crucible, sequentially adding a sodium hydroxide solution and absolute ethyl alcohol in a certain proportion, uniformly stirring, transferring into an oven to be dried at a certain temperature, transferring into a high-temperature tubular furnace, introducing inert gas as protective gas, calcining at a high temperature for a certain time, and naturally cooling to obtain the nitrogen-sulfur double-doped porous carbon material catalyst.
In this embodiment, in the first step, the nitrogen source is one, two or more selected from urea, melamine and L-cysteine; the sulfur source is selected from one, two or more of sodium sulfide, thiourea and L-cysteine; the carbon source is selected from one, two or more of glucose, graphene oxide and cyclodextrin. The temperature in the hydrothermal reaction kettle container is 160-200 ℃, and preferably 160-180 ℃; the reaction time is 8-15 hours, preferably 10-12 hours, and after the hydrothermal reaction is finished, the sample is ground.
In the second step, the temperature is raised to 200-500 ℃ at the rate of 1-8 ℃/min in the high-temperature calcination process, and the temperature is kept for 0.5-2.0 hours.
In the third step, the proportion of the nitrogen-sulfur double-doped carbonized material, 1mol/L sodium hydroxide and absolute ethyl alcohol is (0.05 g-0.2 g): (1 mL-4 mL): (0.2 mL-0.8 mL), preferably (0.11g): 2 mL: 0.4 mL). In the high-temperature calcination process, the temperature is raised to 700-1000 ℃ at the speed of 1-8 ℃/min, the temperature is kept for 1.0-2.0 hours, then the temperature is lowered to 400-500 ℃ at the speed of 10-15 ℃/min, and finally the temperature is naturally cooled to the room temperature.
In the second step and the third step, the inert protective gas is high-purity nitrogen and argon, and the purity is more than or equal to 99.99 percent.
Example 4
The basic structure of the preparation method of the nitrogen-sulfur double-doped porous carbon material catalyst of the embodiment is the same as that of the embodiment 3, and the differences and improvements are as follows: the method comprises the following steps:
example A
(1) Weighing 7.2g by taking glucose as a carbon source, respectively taking 0.36g by taking L-cysteine as a nitrogen source and a sulfur source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle in an oven, preserving the temperature for 12h at 180 ℃, washing a filtered sample by using ultrapure water after the reaction is finished, putting the sample in a culture dish, putting the culture dish in a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample into a quartz glass container (not exceeding 2/3 of the container), and placing the quartz glass containerIs placed in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 ℃ at a heating rate of 5 ℃/min in an atmosphere high-temperature tube furnace, preserving heat for 1h, cooling to 500 ℃ at a cooling rate of 10 ℃/min, and naturally cooling to room temperature to obtain the N-S double-doped porous carbon material, which is recorded as N, S-CSs900-5％-OH。
Example B
(1) Weighing 7.2g by taking glucose as a carbon source, respectively taking 0.72g by taking L-cysteine as a nitrogen source and a sulfur source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle in an oven, preserving the temperature for 12h at 180 ℃, washing a filtered sample by using ultrapure water after the reaction is finished, putting the sample in a culture dish, putting the culture dish in a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 deg.C at a heating rate of 5 deg.C/min, maintaining for 1h, cooling to 500 deg.C at a cooling rate of 10 deg.C/min, and naturally cooling to room temperatureIs a nitrogen-sulfur double-doped porous carbon material, and is marked as N, S-CSs900-10％-OH。
Example C
(1) Weighing 7.2g by taking glucose as a carbon source, respectively taking 1.44g by taking L-cysteine as a nitrogen source and a sulfur source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle in an oven, preserving the temperature for 12h at 180 ℃, washing a filtered sample by using ultrapure water after the reaction is finished, putting the sample in a culture dish, putting the culture dish in a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 ℃ at a heating rate of 5 ℃/min in an atmosphere high-temperature tube furnace, preserving heat for 1h, cooling to 500 ℃ at a cooling rate of 10 ℃/min, and naturally cooling to room temperature to obtain the N-S double-doped porous carbon material, which is recorded as N, S-CSs900-20％-OH。
Example D
(1) Weighing 7.2g by taking glucose as a carbon source, respectively taking 2.88g by taking L-cysteine as a nitrogen source and a sulfur source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle in an oven, preserving the temperature for 12h at 180 ℃, washing a filtered sample by using ultrapure water after the reaction is finished, putting the sample in a culture dish, putting the culture dish in a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 ℃ at a heating rate of 5 ℃/min in an atmosphere high-temperature tube furnace, preserving heat for 1h, cooling to 500 ℃ at a cooling rate of 10 ℃/min, and naturally cooling to room temperature to obtain the N-S double-doped porous carbon material, which is recorded as N, S-CSs900-40％-OH。
Comparative example A
(1) Weighing 7.2g of glucose serving as a carbon source, putting the weighed sample into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the solution into a stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle into an oven, preserving the temperature for 12h in an environment at 180 ℃, washing and filtering the sample by ultrapure water after the reaction is finished, putting the sample into a culture dish, putting the culture dish into a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 ℃ at a heating rate of 5 ℃/min in an atmosphere high-temperature tube furnace, and preserving heat for 1hAfter the heat preservation is finished, the temperature is reduced to 500 ℃ by a temperature reduction rate program of 10 ℃/min and then is naturally reduced to room temperature, namely the non-doped carbon material is recorded as CSs900-OH。
Comparative example B
(1) Weighing 7.2g by taking glucose as a carbon source, weighing 0.357g by taking urea as a nitrogen source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the solution into a stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle into an oven, preserving the temperature for 12h at 180 ℃, washing and filtering a sample by using ultrapure water after the reaction is finished, putting the sample into a culture dish, putting the culture dish into a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 deg.C at a heating rate of 5 deg.C/min, maintaining for 1h, cooling to 500 deg.C at a cooling rate of 10 deg.C/min, and naturally cooling to room temperature to obtain single nitrogen-doped carbon material, denoted as N-CSs900-OH。
Comparative example C
(1) Weighing 7.2g by taking glucose as a carbon source, weighing 2.854g by taking sodium sulfide as a sulfur source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the solution into a stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle into an oven, preserving the temperature for 12h at 180 ℃, washing and filtering a sample by using ultrapure water after the reaction is finished, putting the sample into a culture dish, putting the culture dish into a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out for later use after cooling to room temperature.
(3) Weighing a certain amount of the sample (2) and putting the sample into a customized crucible, and then sequentially adding a 1M NaOH solution and absolute ethyl alcohol according to a certain proportion, wherein the proportion is 0.11 g: 2mL of: 0.4mL, stirring uniformly after all the components are added, and placing the mixture in an oven to be dried at the temperature of 80 ℃. After drying, putting the crucible containing the sample into N2Heating to 900 ℃ at a heating rate of 5 ℃/min in an atmosphere high-temperature tube furnace, preserving heat for 1h, cooling to 500 ℃ at a cooling rate of 10 ℃/min, and naturally cooling to room temperature to obtain the single sulfur-doped carbon material, which is recorded as S-CSs900-OH。
Comparative example D
(1) Weighing 7.2g by taking glucose as a carbon source, respectively taking 0.72g by taking L-cysteine as a nitrogen source and a sulfur source, putting the weighed materials into a beaker, adding 160mL of deionized water, putting the beaker on a magnetic stirrer, stirring for 30min, filling the uniformly stirred solution into a polytetrafluoroethylene lining, putting the stainless steel hydrothermal reaction kettle (200mL), finally putting the reaction kettle in an oven, preserving the temperature for 12h at 180 ℃, washing a filtered sample by using ultrapure water after the reaction is finished, putting the sample in a culture dish, putting the culture dish in a blast drying oven, and drying the sample at 80 ℃ for later use.
(2) Taking a certain amount of the sample (1) and placing the sample in a quartz glass container (not exceeding 2/3 of the container) and placing the quartz glass container in N2And (3) heating to 400 ℃ at the speed of 4 ℃/min in the atmosphere tube furnace, preserving the heat for 60min, and taking out after cooling to room temperature to obtain the nitrogen-sulfur double-doped carbonized material (not subjected to alkali activation) which is recorded as N, S-CSs-10%.
As shown in fig. 1(a), after being activated by sodium hydroxide, the nitrogen-sulfur double-doped carbonized material is mainly in a spherical structure, the diameter of the nitrogen-sulfur double-doped carbonized material is varied from 2 micrometers to 5 micrometers, and the surface of the nitrogen-sulfur double-doped carbonized material is rough and scaly, which may be because the surface of the carbon sphere has a scaly lamellar structure due to gas generated during high-temperature calcination, and this structure results in that the nitrogen-sulfur double-doped porous carbon material has a higher specific surface area and increased catalytic active sites compared with a simple carbon material, which is beneficial to the activation of persulfate on the surface thereof, thereby promoting the degradation of oxytetracycline. As shown in fig. 1(b), the nitrogen-sulfur double-doped carbonized material which is not subjected to the sodium hydroxide alkali activation is spherical, the diameter of the spherical shape is varied from 0.5 micron to 2 microns, and the surface is smooth. As shown in fig. 1(c), the undoped carbon material does not form a regular spherical structure after high-temperature alkali activation.
As shown in fig. 2, there are a peak of C1S (about 283.60 eV), a peak of N1S (about 400.00 eV), a peak of O1S (about 531.93 eV), and a peak of S2p (about 165.65 eV). Strong C, O, N and weak S peaks are shown in the tested spectra, with no peaks of other impurities, confirming successful incorporation of N and S into the C-framework without any other products. The intensity of the peak indicates the content of the element in the material to some extent. There was only a weak peak of S2p in example 1, indicating a low elemental sulfur content.
As shown in FIG. 3(a), the curve of example B exhibits a type I isotherm characteristic according to the International Union of pure and applied chemistry classification, indicating the presence of mesoporous (2-50nm) structures, consistent with the results in the pore size distribution curve, with mostly 3.71nm pore sizes. Isotherm is at P/P0Near 1 is unstable and also exhibits a macroporous structure, and therefore, a relatively broad pore size distribution shows a pore size hierarchical structure. And comparative example A (4306.8 m)2In comparison with example B (1415.9 m)2The specific surface area per g) is significantly reduced, but still at a higher specific surface area, which is likely that the addition of L-cysteine significantly changes the internal structure of the catalyst. As shown in fig. 3(c), the high specific surface area can expose more active sites, so that the adsorption capacity and removal rate are greatly improved. Compared to comparative example a, which was not doped with heteroatoms, L-cysteine not only served as a source of nitrogen and sulfur, but also as a pore structure modifier converting the macropores into mesopores. As shown in FIG. 3(B), while comparing comparative example D and example B which were not subjected to high-temperature activation, the specific surface area and the pore volume were greatly changed from 0.7565m2G and 0.001838m3G to1415.9m2G and 0.7003m3(ii) in terms of/g. Thus, both the high temperature chemical activation and the addition of L-cysteine can alter the pore structure and the distribution of specific surface area. In addition, the formation of a pore structure in the material may also be due to the addition of a basic activator during high temperature activation.
As shown in FIGS. 4(a) and (b), the content of pyridine N is significantly decreased with the increase of the doping amount of L-cysteine, and pyrrole N and graphite N are formed and become dominant. This is due to the restructuring of the N and C atoms resulting in the conversion from pyridine N to pyrrole N and graphite N during high temperature activation. Wherein the N, S-CSs 900-10% -OH obtained in example B contained the highest amount of pyrrole N (49%) and thiophenethiol (60%) (N, S-CSs 900-5% -OH obtained in example A was 44% and 32% respectively, N, S-CSs 900-20% -OH obtained in example C was 38% and 42% respectively, and N, S-CSs 900-40% -OH obtained in example D was 40% and 31% respectively).
As shown in fig. 5(a), the single oxidant Persulfate (PDS) oxidized to remove OTC, and the removal rate was only 17.8% in 90 min. N, S-CSs obtained in example B900The adsorption removal rate of-10% -OH to OTC is only 43.8%. A degradation rate of OTC of up to 97.7% within 90min was observed in the example B + PDS system. This demonstrates that the addition of example B significantly promotes the activation of PDS, and that strong oxidizing reactive species are generated during the reaction process to rapidly degrade OTC. The excellent catalytic performance of example B is attributed to the high content of pyrrole N (0.612 at.%) and pyridine N (0.486 at.%), the electron rich region can efficiently activate the oxidant PDS to generate active radicals. In addition, the adsorption process before the catalytic reaction is also important in the process. The degradation process of OTC in different carbon material + PDS systems is shown in FIG. 5 (b). The comparative example A + PDS system has a 90.39% OTC degradation rate. This is probably due to the high specific surface area of comparative example A (4306.8 m)2/g) allows more active sites to be exposed, facilitating adsorption of OTC and activation of PDS. The comparative example B + PDS system has a degradation rate of 94.4% for OTC, but poor catalytic stability. Comparative example C has a poor catalytic performance, indicating that the sulfur doping element is not an effective active site for the catalyst. Comparative example D has the worst catalytic performance, and the removal rate and reaction rate constants are only 29.1% and 0.0093min-1It is demonstrated that the carbon material which is not subjected to high-temperature alkali activation cannot exhibit excellent catalytic activity. The research results show that the catalytic performance of the material can be optimized only by carrying out nitrogen-sulfur double doping and high-temperature alkali activation.
As shown in FIG. 6, by fitting a linear relationship between lnk and 1/T, the reaction activation energy (Ea) of the example B + PDS system was calculated to be 18.23kJ/mol, much lower than that of the PDS system (38.77kJ/mol), according to the Arrhenius equation, which also indicates that the addition of example B promotes the chemical reaction.
To understand the contribution of different oxidation actives in the example B + PDS system, a free radical quenching experiment was performed to investigate the mechanism of PDS activation and OTC degradation. Two commonly used quenchers methanol (MeOH) and tert-butanol (TBA) were used as SO, respectively4 ·-And. OH, as shown in FIG. 7(a), the example B + PDS system showed 97.7% OTC degradation in 90min without scavenger. When [ MeOH/TBA ]]:[PDS]When the molar ratio of (A) to (B) is up to 1000:1, the inhibition of the catalytic degradation of the OTC is not obvious, and the removal rates respectively reach 90.73% and 84.62%. This indicates that although SO is produced in the process4 ·-And. OH, but their degradation on OTC was not significant. It has been found that the degradation of OTC is also attacked by other active species and that p-BQ can be used as. O2 -The quencher of (1). p-BQ ([ p-BQ) ] in comparison to MeOH and TBA]:[PDS]5) significantly inhibited OTC degradation, with only 49.12% OTC removal in the presence of p-BQ (up to 97.7% without quencher), indicating O2 -Indeed, it is the main reason for the OTC degradation in the example B + PDS system. Some reported studies indicate that non-free radical pathways may also occur during activation of PDS, singlet oxygen ((ii))1O2) Are widely regarded as typical active species in non-radical processes. Also, by using 15mM L-histidine ([ p-BQ ]]:[PDS]As (5) a1O2The quencher was found to be degraded only by 87.91% of OTC within 90min, which indicates that a certain amount of the catalyst is generated during the catalytic process1O2. The above experiment shows that free radicals exist in the process of catalytic degradation of OTC by the B + PDS system in the examplePathways, also non-radical pathways exist, in which O is2 -And1O2principally, of course SO4 ·-And OH. The EPR test is a radical trapping experiment performed with 5, 5-dimethyl-1-pyrroline (DMPO) and 2,2,6, 6-tetramethyl-4-piperidone (TEMP) as spin traps. Use of DMPO for detection O2 -、SO4 ·-And OH, and TEMP for detection1O2. As shown in FIG. 7(b), no peak was detected in the methanol solution of PDS/DMPO, indicating that O.O.was not produced2 -While six characteristic peaks were detected after addition of example B, which was DMPO-. O2 -The characteristics of the adduct. This indicates that the addition of example B activates PDS and generates O2 -. As shown in FIG. 7(c), a peak in the ratio of 1:2:2:1 was detected in the aqueous solution of example B + PDS + DMPO, which was attributed to the DMPO-. OH adduct, indicating the formation of. OH. Similarly, a weak set of peaks around the OH signal is attributed to DMPO-SO4 ·-Adduct showing SO formation4 ·-. As shown in FIG. 7(d), in addition, after example B was added to the PDS + TEMP solution, the peak of the 1:1:1 triplet state signal appeared to be TEMP-1O2This indicates that1O2Is generated. These results are consistent with those found in the quenching experiments.
As shown in fig. 8, the catalytic stability of used example B was tested by collecting it from the waste stream by high speed centrifugation, ethanol and ultra pure water washing treatment. Example B showed excellent catalytic stability, maintaining good catalytic activity during 5 cycles, and maintaining 90.79% of OTC removal after the fifth cycle. The average degradation rate and average reaction rate constant of 5 cycles of the experiment were 92.32% and 2.64X 10-2min-1. Compared with example B, the two catalysts of comparative example a and comparative example B have poor catalytic stability under the same conditions. Comparative example a has a large specific surface area and comparative example B has a high pyrrole N content, although in the first experiment it shows almost the same excellent performance as example B. However, as the number of repeated experiments increased, comparative examples A and BThe active sites of (a) are gradually consumed and occupied, resulting in deterioration of their performance mainly due to a significant decrease in adsorption capacity. This indicates that the adsorption plays an important role in the degradation of OTC in the example B + PDS system.
As shown in FIGS. 9-10, the SEM and Fourier transform IR spectra of example B after five cycles of the experiment were consistent with the original example B structure. This indicates that the surface structure and functional groups of example B did not decrease or significantly change with increasing number of uses and that the active sites are still stable, which is a good indication of the excellent catalytic stability of example B.
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.

Claims (10)

1. A nitrogen-sulfur double-doped porous carbon material catalyst is characterized in that: the porous carbon material comprises a nitrogen-sulfur source and a carbon source in a mass ratio of 1-50%, wherein the carbon source is glucose, and the nitrogen-sulfur source is cysteine.
2. The nitrogen-sulfur double-doped porous carbon material catalyst according to claim 1, wherein: the mass ratio of the nitrogen-sulfur source to the carbon source is 5-40%.
3. The nitrogen-sulfur double-doped porous carbon material catalyst according to claim 1 or 2, wherein: the nitrogen and the sulfur are uniformly distributed on the surface of the porous carbon material, and the aperture of the porous carbon material is 2-50 nm.
4. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 3, comprising the following steps:
the method comprises the following steps: weighing a certain amount of carbon source, nitrogen source and sulfur source, mixing and dispersing in an aqueous solution, transferring to a hydrothermal reaction kettle container, heating to a certain temperature and keeping for a certain time to obtain a carbon material containing carbon, nitrogen and sulfur;
step two, putting the synthesized carbon material containing carbon, nitrogen and sulfur into a quartz glass container, introducing inert gas as protective gas, calcining at high temperature for a certain time, naturally cooling, grinding and crushing to obtain a nitrogen-sulfur double-doped carbonized material;
and step three, putting the synthesized nitrogen-sulfur double-doped carbonized material into a customized crucible, sequentially adding a sodium hydroxide solution and absolute ethyl alcohol in a certain proportion, uniformly stirring, transferring into an oven to be dried at a certain temperature, transferring into a high-temperature tubular furnace, introducing inert gas as protective gas, calcining at a high temperature for a certain time, and naturally cooling to obtain the nitrogen-sulfur double-doped porous carbon material catalyst.
5. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 3, wherein the method comprises the following steps: in the first step, the nitrogen source is selected from one, two or more of urea, melamine and L-cysteine; the sulfur source is selected from one, two or more of sodium sulfide, thiourea and L-cysteine; the carbon source is selected from one, two or more of glucose, graphene oxide and cyclodextrin.
6. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 4, wherein the method comprises the following steps: in the first step, the temperature in the hydrothermal reaction kettle container is 160-200 ℃, the reaction time is 8-15 hours, and after the hydrothermal reaction is finished, the sample is ground.
7. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 4, wherein the method comprises the following steps: in the second step, the temperature is raised to 200-500 ℃ at the rate of 1-8 ℃/min in the high-temperature calcination process, and the temperature is kept for 0.5-2.0 hours.
8. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 4, wherein the method comprises the following steps: in the third step, the proportion of the nitrogen-sulfur double-doped carbonized material, 1mol/L sodium hydroxide and absolute ethyl alcohol is (0.05-0.2 g): (1-4 mL): (0.2-0.8 mL).
9. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 4, wherein the method comprises the following steps: in the third step, the high-temperature calcination process is carried out, wherein the temperature is raised to 700-1000 ℃ at the speed of 1-8 ℃/min, the temperature is kept for 1.0-2.0 hours, then the temperature is lowered to 400-500 ℃ at the speed of 10-15 ℃/min, and finally the high-temperature calcination process is naturally cooled to the room temperature.
10. The method for preparing a nitrogen-sulfur double-doped porous carbon material catalyst according to claim 4, wherein the method comprises the following steps: in the second step and the third step, the inert protective gas is high-purity nitrogen and argon, and the purity is more than or equal to 99.99 percent.
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