CN114272895A - Nitrogen-sulfur-phosphorus co-doped ordered porous biochar and preparation method and application thereof - Google Patents
Nitrogen-sulfur-phosphorus co-doped ordered porous biochar and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses nitrogen-sulfur-phosphorus co-doped ordered porous biochar and a preparation method and application thereof, wherein the ordered porous biochar is doped with nitrogen, sulfur and phosphorus, wherein the atomic percent of nitrogen is 7.1-8.7%, the atomic percent of sulfur is 0.4-1.0%, and the atomic percent of phosphorus is 0.1-1.0%. The nitrogen-sulfur-phosphorus co-doped ordered porous biochar has the advantages of ordered multi-level pore structure, large specific surface area, rich surface oxygen-containing functional groups, high graphitization degree, strong catalytic capability, environmental friendliness and the like, can be used as an activating agent for activating persulfate, can effectively remove organic pollutants in water by effectively activating persulfate, can be widely used for removing organic pollutants in water, and has high use value and good application prospect. Meanwhile, the preparation method has the advantages of simple process, convenient operation, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of materials and the field of organic pollutant treatment, relates to modified ordered porous biochar, a preparation method and application thereof, and particularly relates to nitrogen-sulfur-phosphorus co-doped ordered porous biochar, a preparation method thereof and application of activated persulfate to degradation of organic pollutants.
Background
With the rapid development of industrial and agricultural industries and urban economy in modern society, a large amount of organic pollutants enter a sewage treatment plant along with the discharge of industrial wastewater and domestic sewage, and the treatment load of the sewage treatment plant is greatly increased. In addition, some organic pollutants are migrated and enriched in the natural water environment along with rainwater or surface runoff through the ways of pesticides, fertilizers and the like used in agricultural production, thereby causing great threat to the natural water ecological environment. 2, 4-dichlorophenol is taken as an example. 2, 4-dichlorophenol is an important organic chemical intermediate product and is mainly used for organic synthesis. In the pesticide industry, the method is mainly used for producing the pesticide fenamiphos, the herbicide oxadiazon, the methyl ester weedicide, the 2, 4-dichlorophenoxy series acid and the ester thereof; in the medical industry, the method is used for producing the anthelmintic thiobischlorophenol; in the auxiliary industry, the method is used for producing the mildew preventive TCS. However, 2, 4-dichlorophenol is a cell plasma poison, and its toxic effect is to react with protein in the cell plasma to form denatured protein, which can inactivate the cells. 2, 4-dichlorophenol can invade nerve center and stimulate spinal cord, thus causing general poisoning symptoms. The 2, 4-dichlorophenol can enter the body through various ways such as skin contact, respiratory tract inhalation, oral entry into the digestive tract and the like. The 2, 4-dichlorophenol is not easy to be oxidized and hydrolyzed under normal conditions. The water solubility of 2, 4-dichlorophenol increases its fluidity, so it is easier to permeate into groundwater through the soil layer, causing groundwater pollution. Moreover, 2, 4-dichlorophenol has an accumulating effect, and its concentration in organisms far exceeds its concentration in water.
Based on the above-mentioned hazards, the treatment of wastewater containing organic pollutants (such as 2, 4-dichlorophenol) and polluted natural water is a difficult problem facing the current water treatment technology and requiring treatment urgently. Common treatment methods include adsorption method, membrane separation method, common oxidation method, biological method and the like, but the methods have the defects of complex process flow, high equipment requirement, high cost, damage to microenvironment, low treatment efficiency and the like. The persulfate-based advanced oxidation method is a water treatment method with high treatment efficiency, thorough removal, low cost, convenient operation and high pH tolerance. A great deal of research shows that the persulfate advanced oxidation technology can efficiently remove various organic matters which are difficult to degrade, such as volatile organic matters, endocrine disruptors, medicines, personal care products, perfluorinated compounds and the like. In the system, persulfate is used as an oxidant and is activated under the catalytic action of a catalyst to generate high-activity oxidation free radicals or intermediate active substances, so that target pollutants are further attacked and degraded. Nowadays, metal-based catalysts are widely used for activating persulfates due to their high catalytic activity, but their application is limited by problems such as secondary pollution caused by the dissolution of existing heavy metals. Carbon-based materials are another kind of green catalyst materials with application potential in development, and reduced graphene oxide, carbon nanotubes, nanodiamonds, mesoporous carbon and other carbon-based materials have been proved to be effective in activating persulfate so far, but the high preparation cost still limits the wide application of the catalyst materials.
The biochar material has wide biomass source and simple preparation, and shows application potential, but the currently prepared biochar material still has weak catalytic capability in a persulfate advanced oxidation system, so that the wide application of the biochar material is seriously limited. Therefore, the development of a novel biochar material with an ordered multi-level pore structure, large specific surface area, rich surface oxygen-containing functional groups, high graphitization degree and strong catalytic capability has great significance for improving the treatment effect of a persulfate advanced oxidation system on organic pollutants, particularly 2, 4-dichlorophenol.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide the nitrogen-sulfur-phosphorus co-doped ordered porous biochar with an ordered multi-level pore structure, large specific surface area, rich surface oxygen-containing functional groups, high graphitization degree and strong catalytic capability, further provide a preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar with simple preparation method, easy operation and low cost and application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in activating persulfate to remove organic pollutants in water, organic pollutants in water are removed by activating persulfate through nitrogen, sulfur and phosphorus co-doped ordered porous biochar, so that the method has the advantages of strong adsorption and concerted catalysis capability, high degradation efficiency, high pH tolerance and the like, and has very important significance for efficiently and thoroughly removing the organic pollutants in the water.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the nitrogen-sulfur-phosphorus co-doped ordered porous biochar comprises ordered porous biochar, wherein nitrogen, sulfur and phosphorus are doped in the ordered porous biochar; the atomic percent of nitrogen, sulfur and phosphorus in the ordered porous biochar is 7.1-8.7%, 0.4-1.0% and 0.1-1.0%.
In the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, the atomic percent of phosphorus in the ordered porous biochar is further improved to be 0.1-0.6%.
In the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, the ordered porous biochar is further improved, and the ordered porous biochar contains three pore structures of macropores, mesopores and micropores, wherein the macropores are in an ordered trendAnd penetrates through the whole ordered porous biological carbon; the pore diameter of the macropores is distributed between 0.2 and 0.8 mu m; the pore diameter of the mesopores is distributed between 2nm and 8 nm; the pore diameter of the micropores is distributed between 0.5nm and 2 nm; the specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is 600m2/g～1000m2/g。
As a general technical concept, the invention also provides a preparation method of the azophos-codoped ordered porous biochar, which comprises the following steps:
s1, mixing the shrimp shell, the sulfur source and triphenylphosphine, and grinding to obtain mixed powder;
s2, carbonizing the mixed powder obtained in the step S1 to obtain a shrimp shell biochar material;
s3, performing acid modification on the shrimp shell biochar material obtained in the step S2 to obtain nitrogen, sulfur and phosphorus co-doped ordered porous biochar.
In the above preparation method, the mass ratio of the sulfur source to the shrimp shell in step S1 is further improved to be 0.1-0.5: 1; the sulfur source is bisphenol S; the mass ratio of the triphenylphosphine to the shrimp shells is 0.1-0.5: 1.
In a further improvement of the above preparation method, in step S1, the shrimp shell further comprises the following steps before use: drying shrimp shell, pulverizing, sieving, and making into shrimp shell powder.
In a further improvement of the above preparation method, in step S2, the carbonization is performed under the protection of an inert atmosphere; the temperature rise rate in the carbonization process is 5-10 ℃/min; the carbonization temperature is 700-900 ℃; the carbonization time is 1-3 h.
In step S3, the acid modification step is to mix the shrimp shell biochar material with an acid solution, perform ultrasonic dispersion, and stir; the mass-volume ratio of the shrimp shell biochar material to the acid solution is 1 g: 20 mL-35 mL; the acid solution is a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is 1-2 mol/L; the ultrasonic dispersion time is 5-25 min; the rotating speed of the stirring is 300-650 rpm; the stirring time is 2 h.
As a general technical concept, the invention also provides application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar or the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared by the preparation method in removing organic pollutants in water by activating persulfate.
The application is further improved, and comprises the following steps: mixing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, persulfate and organic pollutants in a water body to carry out an oxidative degradation reaction, and finishing the removal of the organic pollutants in the water body.
In the application, the mass ratio of the nitrogen, sulfur and phosphorus co-doped ordered porous biochar to organic pollutants in a water body containing the organic pollutants is further improved to be 1-5: 1; the mass ratio of the persulfate to the organic pollutants in the organic pollutant water body is 4-10: 1; the persulfate is sodium persulfate; the organic pollutant is 2, 4-dichlorophenol.
In the application, the initial pH value of the organic pollutant water body is further improved to be 2-11; the oxidative degradation reaction is carried out at the rotating speed of 100 rpm-300 rpm; the temperature of the oxidative degradation reaction is 15-35 ℃; the time of the oxidative degradation reaction is 10 min-60 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a nitrogen-sulfur-phosphorus co-doped ordered porous biochar which comprises ordered porous biochar, wherein the ordered porous biochar is doped with nitrogen, sulfur and phosphorus, wherein the atomic percent of nitrogen in the ordered porous biochar is 7.1-8.7%, the atomic percent of sulfur is 0.4-1.0%, and the atomic percent of phosphorus is 0.1-1.0%. Compared with the conventional porous biochar, the ordered porous biochar adopted by the invention has an ordered macroporous structure, a more abundant porous structure, a larger specific surface area and a higher graphitization degree, so that organic pollutants can be adsorbed and adsorbed more quickly and efficiently, a higher mass transfer rate can be obtained, more catalytic sites can be provided, and meanwhile, electrons can be transferred more quickly and efficiently; on the basis, a proper amount of sulfur and phosphorus are codoped into the primary nitrogen-doped porous biochar, the phosphorus with low electronegativity, the sulfur with similar electronegativity and the nitrogen with high electronegativity (compared with the electronegativity of carbon) can be interacted through bonding, induction and the like, the electron distribution condition expressed by the porous biochar is regulated and controlled, the surface of the biochar is further induced to form a micro-electric field, the number of surface catalytic sites is enriched, meanwhile, the doped phosphorus can further improve the graphitization degree of the biochar, and the catalytic performance of the biochar is synergistically improved. However, when the amount of doped sulfur and phosphorus is too large, the electron distribution balance in the biochar carbon skeleton is broken by the excessive sulfur and phosphorus, the doped sulfur and phosphorus mainly exist in the form of oxides, and the electron transfer function between the biochar carbon skeleton and the oxidant is reduced by the excessive oxygen-containing functional groups through effects of steric hindrance and the like, so that the catalytic activity is reduced. The nitrogen-sulfur-phosphorus-codoped ordered porous biochar has the advantages of ordered multi-level pore structure, large specific surface area, rich surface oxygen-containing functional groups, high graphitization degree, strong catalytic capability, environmental friendliness and the like, can be used as an activating agent for activating persulfate, can effectively remove organic pollutants in water by effectively activating persulfate, and has high use value and good application prospect.
(2) The invention also provides a preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, which is prepared by taking shrimp shells, a sulfur source and triphenylphosphine as raw materials through pyrolysis calcination and acid modification, and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar which has an ordered multi-level pore structure, a large specific surface area, rich surface oxygen-containing functional groups, a high graphitization degree and a strong catalytic capability is obtained. In the invention, the shrimp shell is urban organic solid waste, and is converted into the biochar functional material, so that not only is the disposal of the waste realized, but also the prepared biochar functional material can be used for environmental pollution treatment, and the method is a win-win strategy. Meanwhile, the shrimp shell is used as a raw material and contains rich nitrogen sources, so that the nitrogen-doped ordered porous biochar can be obtained without additionally adding the nitrogen sources. On this basis, mix the shrimp shell with sulphur source, triphenylphosphine and carry out the carbonization, not only can successfully dope into gained charcoal material with two kinds of elements of sulphur and phosphorus respectively, and they contain abundant benzene ring structure in addition, can effectively promote the graphitization degree of doping material after the codoping, promote the electron transfer ability and the catalytic performance of nitrogen sulphur phosphorus codoped ordered porous charcoal in coordination. In addition, the acid modification can remove the native calcium carbonate and other substances in the shrimp shell biochar and endow the shrimp shell biochar with rich macroporous, mesoporous and mesoporous structures. More importantly, phosphorus doping based on triphenylphosphine can induce the macropores in the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to be in an ordered trend, so that the macropores penetrate through the whole ordered porous carbon material, the mass transfer rate of a reaction system is improved, meanwhile, the abundance of oxygen-containing functional groups on the surface, the abundance of pore structures and the abundance of surface catalytic sites of the azophos-codoped ordered porous biochar can be improved, and finally, a more ordered porous hierarchical structure, a larger specific surface area, more abundant oxygen-containing functional groups on the surface and stronger catalytic capability are obtained, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar can efficiently activate persulfate, can efficiently remove organic pollutants in water in more time, has performance remarkably superior to that of non-co-doped biochar, and has good application prospect in water body remediation of actual organic pollutants. Meanwhile, the preparation method provided by the invention has the advantages of simple process, convenience in operation, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(3) The invention also provides application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate, wherein the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is applied to an advanced oxidation system of persulfate for the first time through direct electron transfer and singlet oxygen leading (C)1O2) Is supplemented with a superoxide anion radical (O)2·-) The dominant free radical path can quickly and effectively realize the degradation of the 2, 4-dichlorophenol in the water body, 99 percent of the 2, 4-dichlorophenol (the initial concentration is 100mg/L) can be removed within 30min of reaction, and the adsorption synergistic catalytic capability is strongThe method has the advantages of high degradation efficiency, high degradation rate, high pH tolerance and the like, and has obvious advantages in the aspect of removing organic pollutants in water. Meanwhile, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar mainly contains six elements such as C, H, O, N, S, P and the like, does not contain metal elements, and does not have the risks of secondary pollution such as metal dissolution and the like. Therefore, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar has the advantages of simple preparation, low cost, strong catalytic performance, strong anti-interference capability, good dispersibility, strong stability and easy recovery and reuse, and is a novel environmental-friendly catalytic material for activating persulfate, which can be widely applied and has excellent catalytic performance.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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.
Fig. 1 is a transmission electron microscope image of undoped modified shrimp shell biochar (a) and nitrogen, sulfur and phosphorus co-doped ordered porous biochar (b, c) prepared in example 1 of the present invention.
Fig. 2 is a nitrogen adsorption and desorption isotherm graph of undoped modified shrimp shell biochar and nitrogen, sulfur and phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention.
Fig. 3 is a pore size distribution diagram of undoped modified shrimp shell biochar and nitrogen, sulfur and phosphorus co-doped ordered porous biochar prepared in example 1 of the invention.
Fig. 4 is a peak chart of the N1s element of the undoped modified shrimp shell biochar prepared in example 1 of the present invention and the nitrogen sulfur phosphorus co-doped ordered porous biochar.
Fig. 5 is a time-removal rate relationship diagram corresponding to the case where different activating materials activate persulfate to remove 2, 4-dichlorophenol in a water body in example 4 of the present invention.
FIG. 6 is a graph showing the degradation effect of persulfate on 2, 4-dichlorophenol activated by nitrogen, sulfur and phosphorus co-doped ordered porous biochar under different pH conditions in example 5 of the present invention.
FIG. 7 is a graph showing the degradation effect of nitrogen, sulfur and phosphorus co-doped ordered porous biochar activated persulfate on 2, 4-dichlorophenol in different dosages in example 6 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and instruments used in the following examples are commercially available and the starting materials were analytically pure. In the following examples, unless otherwise specified, the data obtained are the average of three or more replicates.
Example 1:
the nitrogen-sulfur-phosphorus co-doped ordered porous biochar comprises ordered porous biochar, wherein nitrogen, sulfur and phosphorus are doped in the ordered porous biochar, wherein the atomic percent of nitrogen in the ordered porous biochar is 7.42%, the atomic percent of sulfur is 0.47%, and the atomic percent of phosphorus is 0.48%.
In the embodiment, the ordered porous biochar comprises three pore structures of macropores, mesopores and micropores, wherein the macropores are in an ordered trend and penetrate through the whole ordered porous biochar, the pore diameter of the macropores is distributed between 0.2 and 0.8 mu m, the pore diameter of the mesopores is distributed between 2 and 8nm, and the pore diameter of the micropores is distributed between 0.5 and 2 nm. The specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is 971.3m2/g。
In this embodiment, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is prepared by taking shrimp shells, a sulfur source and triphenylphosphine as raw materials and performing pyrolysis calcination (carbonization) and acid modification, and mainly comprises elements such as carbon, oxygen, nitrogen, sulfur and phosphorus.
The preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar comprises the following steps:
(1) doping pretreatment of waste shrimp shells: drying and crushing the waste shrimp shells, and sieving the crushed waste shrimp shells through a 120-mesh sieve to obtain undoped pretreated shrimp shell powder; 1g of shrimp shell powder was taken, 0.25g of bisphenol S and 0.5g of triphenylphosphine were added to each of the shrimp shell powder, and the mixture was ground to obtain a waste doped pretreated shrimp shell powder (mixed powder).
(2) Preparing shrimp shell biochar: respectively placing the non-doped pretreated shrimp shell powder and the doped pretreated waste shrimp shell powder obtained in the step (1) into a tube furnace, heating to 800 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of flowing nitrogen, carbonizing at constant temperature for 2h, and taking out after natural cooling to obtain the non-doped pretreated shrimp shell biochar and the doped pretreated shrimp shell biochar.
(3) Modification of shrimp shell biochar: and (3) respectively adding 1g of the undoped pretreated shrimp shell biochar prepared in the step (2) and the doped pretreated shrimp shell biochar into 40mL of hydrochloric acid solution with the concentration of 2mol/L, performing ultrasonic dispersion for 10min (the ultrasonic dispersion can be performed for 5 min-25 min), then placing the mixture at room temperature and stirring the mixture at the rotating speed of 350rpm, and performing reaction treatment for 2h to finish the acid modification of the shrimp shell biochar. Filtering the reacted mixed solution, washing the solid matter obtained by filtering with deionized water until the solid matter is neutral, and drying the solid matter at the temperature of 80 ℃ for 24 hours (drying at the temperature of 70-100 ℃ for 18-26 hours) to respectively obtain the undoped modified shrimp shell biochar and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar.
Transmission electron microscopy imaging was performed on the undoped modified shrimp shell biochar prepared in example 1 and the nitrogen sulfur phosphorus co-doped ordered porous biochar, and the results are shown in fig. 1. Fig. 1 is a transmission electron microscope image of undoped modified shrimp shell biochar (a) and nitrogen, sulfur and phosphorus co-doped ordered porous biochar (b, c) prepared in example 1 of the present invention. As can be seen from FIG. 1, the shrimp shell powder has been completely carbonized into biochar; compared with the non-doped modified shrimp shell biochar, the modified nitrogen-sulfur-phosphorus-doped ordered porous biochar has an obvious pore structure, large pores with similar sizes, uniform distribution and obvious ordered trend and penetrate through the whole biochar body, the pore size of the large pores is distributed between 0.2 and 0.8 mu m, the pore size of the mesopores is distributed between 2 and 8nm, and the pore size of the micropores is distributed between 0.5 and 2 nm. In addition, as can also be seen from fig. 1, the modified nitrogen-sulfur-phosphorus-doped ordered porous biochar has obvious graphite stripes, which indicates that the graphitization degree is high.
Undoped modified shrimp shell biochar prepared in example 1, nitrogen, sulfur and phosphorus co-doped ordered polyThe pore biochar is characterized by nitrogen adsorption and desorption, as shown in figure 2. Fig. 2 is a nitrogen adsorption and desorption isotherm graph of undoped modified shrimp shell biochar and nitrogen, sulfur and phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention. Fig. 3 is a pore size distribution diagram of undoped modified shrimp shell biochar and nitrogen, sulfur and phosphorus co-doped ordered porous biochar prepared in example 1 of the invention. As can be seen from FIGS. 2 and 3, compared with the non-doped modified shrimp shell biochar, the pore structure of the modified nitrogen-sulfur-phosphorus co-doped ordered porous biochar is obviously increased, and the specific surface area is 543.6m2The/g is increased to 971.6m2The number of micropores and mesopores is obviously increased; the ordered macroporous in figure 1 shows that the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared by the invention is a typical ordered multi-level pore structure.
Elemental composition analysis was performed on the undoped modified shrimp shell biochar prepared in example 1, and the nitrogen sulfur phosphorus co-doped ordered porous biochar, as shown in table 1. Table 1 shows the atomic percentages of the elements in the undoped modified shrimp shell biochar prepared in example 1 of the present invention and the nitrogen, sulfur and phosphorus co-doped ordered porous biochar. As can be seen from table 1, the elements contained in the undoped modified shrimp shell biochar include carbon, oxygen and nitrogen, while the nitrogen, sulfur and phosphorus co-doped ordered porous biochar of the present invention contains three elements of carbon, oxygen and nitrogen, and two elements of sulfur and phosphorus are newly added, which indicates that sulfur and phosphorus are successfully doped, and the prepared biochar is nitrogen, sulfur and phosphorus co-doped biochar. In addition, as can be seen from table 1, the atomic percentages of nitrogen, sulfur and phosphorus in the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention were 7.42%, 0.47% and 0.48%, respectively.
TABLE 1 atomic percentages of elements in undoped modified shrimp shell biochar and nitrogen, sulfur and phosphorus co-doped ordered porous biochar
| Material | C | O | N | S | P |
| Undoped modified shrimp shell biochar | 85.78 | 5.58 | 8.64 | - | - |
| Nitrogen-sulfur-phosphorus co-doped ordered porous biochar | 84.82 | 6.81 | 7.42 | 0.47 | 0.48 |
In Table 1, "-" indicates no detection.
The undoped modified shrimp shell biochar prepared in example 1 and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar were subjected to N1s element peak separation characterization (X-ray photoelectron spectroscopy), as shown in fig. 4. Fig. 4 is a peak chart of the N1s element of the undoped modified shrimp shell biochar prepared in example 1 of the present invention and the nitrogen sulfur phosphorus co-doped ordered porous biochar. As shown in FIG. 4, the nitrogen elements in the undoped modified shrimp shell biochar and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar have three occurrence forms, namely pyridine nitrogen (398.3eV), pyrrole nitrogen (400.2eV) and graphite nitrogen (401.8 eV). In addition, as can be seen from fig. 4, the peak of graphite nitrogen (401.8eV) in the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of the present invention is enhanced compared to the undoped modified shrimp shell biochar, indicating that the graphitization degree thereof is increased; meanwhile, a peak belonging to the nitrogen oxide (403.2eV) was newly added, indicating that the surface thereof contains more oxygen-containing functional groups.
The test data show that the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared by the method has the advantages of an ordered multi-level pore structure, large specific surface area, rich surface oxygen-containing functional groups, high graphitization degree, strong catalytic capability and the like, is a novel environment-friendly catalytic material which can be widely applied and has excellent catalytic performance and is used for activating persulfate, and has advantages in activating persulfate and degrading and removing organic pollutants in water.
Example 2:
a nitrogen sulfur phosphorus co-doped ordered porous biochar, which is substantially the same as the nitrogen sulfur phosphorus co-doped ordered porous biochar of example 1, except that: the atomic percent of nitrogen, sulfur and phosphorus in the nitrogen, sulfur and phosphorus co-doped ordered porous biochar of example 2 is 7.87%, the atomic percent of sulfur is 0.45%, and the atomic percent of phosphorus is 0.13%; the specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 2 is 632.3m2/g。
The preparation method of the nitrogen, sulfur and phosphorus co-doped ordered porous biochar in the embodiment is basically the same as that of embodiment 1, and the difference is only that: in step (1) of the production method of example 2, triphenylphosphine was used in an amount of 0.25 g.
Example 3:
a nitrogen sulfur phosphorus co-doped ordered porous biochar, which is substantially the same as the nitrogen sulfur phosphorus co-doped ordered porous biochar of example 1, except that: example 3 atomic percent of nitrogen, sulfur and phosphorus co-doped ordered porous biochar is 7.37%, 0.44% sulfur and 0.92% phosphorus; example 3 specific surface area of nitrogen, sulfur and phosphorus co-doped ordered porous biochar is 1215.3m2/g。
The preparation method of the nitrogen, sulfur and phosphorus co-doped ordered porous biochar in the embodiment is basically the same as that of embodiment 1, and the difference is only that: in step (1) of the preparation process of example 3, triphenylphosphine was used in an amount of 1 g.
Comparative example 1:
a nitrogen-sulfur co-doped ordered porous biochar, which is substantially the same as the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 1, except that: comparative example 1 atomic percent of nitrogen and sulfur in the nitrogen and sulfur co-doped ordered porous biochar is 7.44%, and atomic percent of sulfur is 0.60%; comparative example 1 specific surface area of nitrogen and sulfur co-doped ordered porous biochar is 550.7m2/g。
The preparation method of the nitrogen and sulfur co-doped ordered porous biochar of the comparative example 1 is basically the same as the preparation method of the example 1, and only the difference is that: comparative example 1 in step (1) of the preparation method, triphenylphosphine was not added.
Comparative example 2:
a nitrogen-phosphorus co-doped ordered porous biochar, which is substantially the same as the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 1, except that: comparative example 2 atomic percent of nitrogen and phosphorus in the nitrogen-phosphorus co-doped ordered porous biochar is 7.56%, and atomic percent of phosphorus is 0.24%; comparative example 2 specific surface area of nitrogen-phosphorus co-doped ordered porous biochar is 783.1m2/g。
The preparation method of the nitrogen-phosphorus co-doped ordered porous biochar is basically the same as that of example 1, and the difference is only that: comparative example 2 in step (1) of the production process, bisphenol S was not added.
Example 4:
the application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate specifically comprises the following steps: the method for activating sodium persulfate to degrade 2, 4-dichlorophenol in water by utilizing nitrogen, sulfur and phosphorus co-doped ordered porous biochar comprises the following steps:
adding the nitrogen-sulfur-phosphorus-codoped ordered porous biochar and persulfate prepared in the example 1 into a 2, 4-dichlorophenol solution (the pH is 5.98) with the initial concentration of 100mg/L according to the mass ratio of 2, 4-dichlorophenol in the nitrogen-sulfur-phosphorus-codoped ordered porous biochar to 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution of 2, 4-dichlorophenol solution of 2.5: 1, carrying out oxidative degradation for 30min under the conditions of 160rpm and 25 ℃, carrying out solid-liquid separation after the reaction is finished, and recovering the nitrogen-sulfur-phosphorus-codoped ordered porous biochar.
In this example, the concentration of 2, 4-dichlorophenol was measured by sampling at 0min, 2min, 5min, 10min, 20min, and 30min after the oxidative degradation reaction was performed, and the influence of different times on the removal effect of 2, 4-dichlorophenol was calculated.
For comparison effect, the undoped shrimp shell biochar prepared in example 1, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in examples 2-3, the nitrogen-sulfur co-doped ordered porous biochar prepared in comparative example 1, and the nitrogen-phosphorus co-doped ordered porous biochar in comparative example 2 are used for activating persulfate to remove 2, 4-dichlorophenol in water according to the above steps, and the catalytic degradation effect is calculated, and the result is shown in fig. 5.
Fig. 5 is a time-removal rate relationship diagram corresponding to the case where different activating materials activate persulfate to remove 2, 4-dichlorophenol in a water body in example 4 of the present invention. In FIG. 5, a is the undoped modified shrimp shell biochar of example 1, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 78.9%, b is the nitrogen sulfur phosphorus co-doped ordered porous biochar of example 1, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 99.3%, c is the nitrogen sulfur phosphorus co-doped ordered porous biochar of example 2, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 92.8%, d is the nitrogen sulfur phosphorus co-doped ordered porous biochar of example 3, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 88.9%, e is the nitrogen sulfur co-doped ordered porous biochar of comparative example 1, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 45.6%, f is the nitrogen phosphorus co-doped ordered porous biochar of comparative example 2, the removal efficiency of the 2, 4-dichlorophenol after 30min of oxidative degradation is 82.3%. As can be seen from fig. 5, compared with the non-doped modified shrimp shell biochar, the nitrogen-phosphorus co-doped ordered porous biochar in examples 1 and 2 has significantly improved ability to activate persulfate and degrade 2, 4-dichlorophenol, and the catalytic ability increases with the increase of the co-doping amount. Compared with the undoped modified shrimp shell biochar, the catalytic degradation capability of the nitrogen-sulfur co-doped ordered porous biochar in the comparative example 1 is obviously reduced, and the catalytic performance of the nitrogen-phosphorus co-doped ordered porous biochar in the comparative example 2 is slightly improved. The result shows that the nitrogen-sulfur-doped or nitrogen-phosphorus-doped ordered porous biochar can not obviously improve the catalytic performance of the undoped modified shrimp shell biochar, and the excellent performance of the nitrogen-sulfur-phosphorus-codoped ordered porous biochar is derived from the synergistic promotion effect among multiple doping elements of nitrogen, phosphorus and sulfur. Therefore, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar activated persulfate prepared by the method disclosed by the invention has excellent performance of degrading organic pollutants in water.
Example 5:
the application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate specifically comprises the following steps: the method for activating sodium persulfate to degrade 2, 4-dichlorophenol in water by utilizing nitrogen, sulfur and phosphorus co-doped ordered porous biochar comprises the following steps:
according to the mass ratio of the nitrogen-sulfur-phosphorus-codoped ordered porous biochar to 2, 4-dichlorophenol in a 2, 4-dichlorophenol solution of 2.5: 1 and the mass ratio of persulfate to 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution of 10: 1, the nitrogen-sulfur-phosphorus-codoped ordered porous biochar and persulfate in the example 1 are respectively added into the 2, 4-dichlorophenol solution (the initial concentration of the solution is 100mg/L) with the pH values of 2.14, 3.95, 5.98, 8.02 and 10.35, and are subjected to oxidative degradation for 30min under the conditions of 160rpm and 25 ℃, solid-liquid separation is carried out after the reaction is finished, and the nitrogen-sulfur-phosphorus-codoped ordered porous biochar is recovered.
In this example, the concentration of 2, 4-dichlorophenol was measured by sampling at 0min, 2min, 5min, 10min, 20min, and 30min after the oxidative degradation reaction, and the influence of different times on the removal effect of 2, 4-dichlorophenol was calculated, and the result is shown in fig. 6.
FIG. 6 is a graph showing the degradation effect of persulfate on 2, 4-dichlorophenol activated by nitrogen, sulfur and phosphorus co-doped ordered porous biochar under different pH conditions in example 5 of the present invention. As can be seen from fig. 6, the removal rates of 2, 4-dichlorophenol were 94.1%, 98.5%, 99.3%, 98.2% and 98.7% at pH values of 2.14, 3.95, 5.98, 8.02 and 10.35, respectively. Therefore, when the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is used for activating persulfate to degrade organic pollutants, the 2, 4-dichlorophenol can be rapidly and efficiently degraded under acidic and weakly acidic conditions, the 2, 4-dichlorophenol can be rapidly degraded under alkaline conditions, the 2, 4-dichlorophenol can be effectively and rapidly degraded, and the method has a good application prospect in actual 2, 4-dichlorophenol wastewater treatment.
Example 6:
the application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate specifically comprises the following steps: the method for activating sodium persulfate to degrade 2, 4-dichlorophenol in water by utilizing nitrogen, sulfur and phosphorus co-doped ordered porous biochar comprises the following steps:
according to the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to 2, 4-dichlorophenol in a 2, 4-dichlorophenol solution of 0:1, 1.5:1, 2.5: 1 and 3.5:1, the mass ratio of persulfate to 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution of 10: 1, respectively adding the nitrogen-sulfur-phosphorus co-doped ordered porous biochar and persulfate in the example 1 into the 2, 4-dichlorophenol solution with the initial concentration of 100mg/L, carrying out oxidative degradation for 30min at 160rpm and 25 ℃, carrying out solid-liquid separation after the reaction is finished, and recovering the nitrogen-sulfur-phosphorus co-doped ordered porous biochar.
In this example, the concentration of 2, 4-dichlorophenol was measured by sampling at 0min, 2min, 5min, 10min, 20min, and 30min after the oxidative degradation reaction, and the influence of different times on the removal effect of 2, 4-dichlorophenol was calculated, and the result is shown in fig. 7.
FIG. 7 is a graph showing the degradation effect of nitrogen, sulfur and phosphorus co-doped ordered porous biochar activated persulfate on 2, 4-dichlorophenol in different dosages in example 6 of the present invention. As can be seen from FIG. 7, when only persulfate does not have the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in the system, 2, 4-dichlorophenol is hardly degraded; when the nitrogen-sulfur-phosphorus-codoped ordered porous biochar is added into the system, the 2, 4-dichlorophenol is rapidly oxidized and degraded, and the removal rate of the system to the 2, 4-dichlorophenol is increased along with the increased adding amount of the nitrogen-sulfur-phosphorus-codoped ordered porous biochar until the 2, 4-dichlorophenol is removed by 100%; wherein when the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution is 0:1, 1.5:1, 2.5: 1 and 3.5:1, the removal rate of the 2, 4-dichlorophenol is 9.4%, 70.3%, 99.3% and 99.8% respectively.
The results show that the nitrogen-sulfur-phosphorus co-doped ordered porous biochar has the advantages of ordered multi-level pore structure, large specific surface area, rich oxygen-containing functional groups on the surface, high graphitization degree, strong catalytic capability, environmental friendliness and the like, can be used as an activating agent for activating persulfate, can effectively remove organic pollutants in water by effectively activating persulfate, and has high use value and good application prospect.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. The nitrogen-sulfur-phosphorus co-doped ordered porous biochar is characterized by comprising ordered porous biochar, wherein the ordered porous biochar is doped with nitrogen, sulfur and phosphorus; the atomic percent of nitrogen, sulfur and phosphorus in the ordered porous biochar is 7.1-8.7%, 0.4-1.0% and 0.1-1.0%.
2. The nitrogen-sulfur-phosphorus co-doped ordered porous biochar according to claim 1, wherein the atomic percent of phosphorus in the ordered porous biochar is 0.1-0.6%.
3. The nitrogen-sulfur-phosphorus co-doped ordered porous biochar according to claim 1 or 2, which is characterized by comprising three pore structures, namely macropores, mesopores and micropores, wherein the macropores are in an ordered trend and penetrate through the whole ordered porous biochar; the pore diameter of the macropores is distributed between 0.2 and 0.8 mu m; the pore diameter of the mesopores is distributed between 2nm and 8 nm; the pore diameter of the micropores is distributed between 0.5nm and 2 nm; the specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is 600m2/g～1000m2/g。
4. The preparation method of the nitrogen, sulfur and phosphorus co-doped ordered porous biochar as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
s1, mixing the shrimp shell, the sulfur source and triphenylphosphine, and grinding to obtain mixed powder;
s2, carbonizing the mixed powder obtained in the step S1 to obtain a shrimp shell biochar material;
s3, performing acid modification on the shrimp shell biochar material obtained in the step S2 to obtain nitrogen, sulfur and phosphorus co-doped ordered porous biochar.
5. The preparation method according to claim 4, wherein in step S1, the mass ratio of the sulfur source to the shrimp shells is 0.1-0.5: 1; the sulfur source is bisphenol S; the mass ratio of the triphenylphosphine to the shrimp shells is 0.1-0.5: 1.
6. The preparation method according to claim 4 or 5, wherein the shrimp shells further comprise the following treatments before use in step S1: drying shrimp shell, pulverizing, sieving, and making into shrimp shell powder;
in step S2, the carbonization is performed under the protection of an inert atmosphere; the temperature rise rate in the carbonization process is 5-10 ℃/min; the carbonization temperature is 700-900 ℃; the carbonization time is 1-3 h;
in the step S3, the acid modification is to mix the shrimp shell biochar material with an acid solution, perform ultrasonic dispersion and stir; the mass-volume ratio of the shrimp shell biochar material to the acid solution is 1 g: 20 mL-35 mL; the acid solution is a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is 1-2 mol/L; the ultrasonic dispersion time is 5-25 min; the rotating speed of the stirring is 300-650 rpm; the stirring time is 2 h.
7. Application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar as claimed in any one of claims 1 to 3 or the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared by the preparation method as claimed in any one of claims 4 to 6 in removing organic pollutants in water by activating persulfate.
8. Use according to claim 7, characterized in that it comprises the following steps: mixing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, persulfate and organic pollutants in a water body to carry out an oxidative degradation reaction, and finishing the removal of the organic pollutants in the water body.
9. The application of the azophos-codoped ordered porous biochar as claimed in claim 8 is characterized in that the mass ratio of azophos-codoped ordered porous biochar to organic pollutants in a water body containing the organic pollutants is 1-5: 1; the mass ratio of the persulfate to the organic pollutants in the organic pollutant water body is 4-10: 1; the persulfate is sodium persulfate; the organic pollutant is 2, 4-dichlorophenol.
10. The use according to claim 9, wherein the initial pH of the body of organic contaminant water is 2 to 11; the oxidative degradation reaction is carried out at the rotating speed of 100 rpm-300 rpm; the temperature of the oxidative degradation reaction is 15-35 ℃; the time of the oxidative degradation reaction is 10 min-60 min.
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