CN114272895B - 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 a nitrogen-sulfur-phosphorus co-doped ordered porous biochar, a preparation method and application thereof, wherein the ordered porous biochar is doped with nitrogen, sulfur and phosphorus, the atomic percent of the nitrogen is 7.1% -8.7%, the atomic percent of the sulfur is 0.4% -1.0%, and the atomic percent of the 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, green and environment-friendly property and the like, can be used as an activator for activating persulfate, can effectively activate persulfate to effectively remove organic pollutants in water, 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 a modified ordered porous biochar, a preparation method and application thereof, and in particular relates to a nitrogen-sulfur-phosphorus co-doped ordered porous biochar, a preparation method thereof and application of activated persulfate to degrade organic pollutants.
Background
With the high-speed development of modern society industry and agriculture and urban economy, 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 migrate and enrich in natural water environment along with rainwater or surface runoff through pesticide, chemical fertilizer and other approaches used in agricultural production, thereby causing great threat to natural water ecological environment. Take 2, 4-dichlorophenol as an example. 2, 4-dichlorophenol is an important intermediate product of organic chemical industry and is mainly used for organic synthesis. In the pesticide industry, the method is mainly used for producing pesticide fenphos, herbicide oxadiazon, methyl ester herbicide, 2, 4-dichlorophenoxy acid and esters thereof; in the pharmaceutical industry, for the production of the anthelmintic thiodichlorophenol; in the auxiliary industry, is used for producing the mildew preventive TCS. However, 2, 4-dichlorophenol is a cell plasma poison and has a toxic effect of reacting reversely and biochemically with proteins in the cell plasma to form denatured proteins, thereby inactivating the cells. 2, 4-dichlorophenol can invade the nerve center, irritate the spinal cord, and cause systemic toxic symptoms. The 2, 4-dichlorophenol can be introduced into the body through various ways such as percutaneous contact, respiratory tract inhalation, oral entry into the digestive tract and the like. 2, 4-dichlorophenol is not easy to oxidize and difficult to hydrolyze under normal conditions. The water solubility of the 2, 4-dichlorophenol increases the fluidity of the 2, 4-dichlorophenol, so that the 2, 4-dichlorophenol is easier to permeate into underground water through a soil layer, and the underground water is polluted. Furthermore, 2, 4-dichlorophenol has an accumulating effect, and its concentration in organisms is far exceeding its concentration in water.
Based on the above hazards, the treatment of wastewater containing organic pollutants (such as 2, 4-dichlorophenol) and polluted natural water bodies is a difficult problem facing the current water treatment technology and needing treatment. Common treatment methods include adsorption, membrane separation, common oxidation, biological methods, etc., but these methods have the disadvantages of complex process flow, high equipment requirements, high cost, destruction of microenvironment, low treatment efficiency, etc. The advanced oxidation method based on persulfate is a water treatment method with high treatment efficiency, thorough removal, low cost, convenient operation and high pH tolerance. Numerous studies have shown that persulfate advanced oxidation techniques can efficiently remove a variety of refractory organics such as volatile organics, endocrine disruptors, pharmaceutical and personal care products, perfluorinated compounds, and the like. In this system, persulfate is used as an oxidant, and is activated under the catalysis of a catalyst to generate high-activity oxidation free radicals or intermediate active substances, so as to further attack and degrade target pollutants. Nowadays, metal-based catalysts are widely used for the activation of persulfates due to their efficient catalytic activity, but their application is limited by the problems of secondary pollution caused by the dissolution of heavy metals, etc. Carbon-based materials are another type of green catalyst materials with application potential under development, and so far, reduced graphene oxide, carbon nanotubes, nanodiamond, mesoporous carbon and other carbon-based materials have been proven to be effective in activating persulfates, but their high preparation cost still limits their wide application.
The biochar material has wide biomass source and simple preparation, and has application potential, but the existing prepared biochar material has weaker catalytic capability in a persulfate advanced oxidation system, which severely limits the wide application of the biochar material. Therefore, the novel biochar material with ordered multilevel pore structure, large specific surface area, rich surface oxygen-containing functional groups, high graphitization degree and strong catalytic capability is developed, and has great significance for improving the treatment effect of a persulfate advanced oxidation system for treating organic pollutants, especially 2, 4-dichlorophenol.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides 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, strong catalytic capability, a preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, which is simple in preparation method, easy to operate and low in cost, and application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in a water body by activating persulfate, and has very important significance in removing the organic pollutants in the water body efficiently and thoroughly by activating persulfate through utilizing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar.
In order to solve the technical problems, the invention adopts the following technical scheme:
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 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%.
The nitrogen-sulfur-phosphorus co-doped ordered porous biochar is further improved, wherein the atomic percentage of phosphorus in the ordered porous biochar is 0.1% -0.6%.
The nitrogen-sulfur-phosphorus co-doped ordered porous biochar is further improved, wherein the ordered porous biochar comprises three pore structures of macropores, mesopores and micropores, and 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 mesoporous is distributed between 2nm and 8nm; the pore diameter distribution of the micropores is 0.5 nm-2 nm; the specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is 600m 2 /g～1000m 2 /g。
As a general technical conception, the invention also provides a preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, which comprises the following steps:
s1, mixing shrimp shells, sulfur sources 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, carrying out acid modification on the shrimp shell biochar material obtained in the step S2 to obtain the nitrogen-sulfur-phosphorus co-doped ordered porous biochar.
In the preparation method, which is further improved, in the step S1, the mass ratio of the sulfur source to the shrimp shell is 0.1-0.5:1; the sulfur source is bisphenol S; the mass ratio of the triphenylphosphine to the shrimp shell is 0.1-0.5:1.
In a further improved preparation method, in step S1, the shrimp shell further comprises the following treatments before use: drying shrimp shell, pulverizing, sieving, and making into shrimp shell powder.
In the preparation method, further improved, in the step S2, the carbonization is performed under the protection of inert atmosphere; the heating rate in the carbonization process is 5-10 ℃/min; the carbonization temperature is 700-900 ℃; the carbonization time is 1-3 h.
In the preparation method, further improved, in the step S3, the acid modification is carried out by mixing the shrimp shell biochar material with an acid solution, carrying out ultrasonic dispersion and stirring; the mass volume ratio of the shrimp shell biochar material to the acid solution is 1g to 20 mL-35 mL; the acid solution is hydrochloric acid solution or sulfuric acid solution; the concentration of the acid solution is 1 mol/L-2 mol/L; the ultrasonic dispersion time is 5-25 min; the rotation speed of the stirring is 300 rpm-650 rpm; the stirring time is 2h.
As a general technical conception, 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 body by activating persulfate.
The above application, further improved, comprising the steps of: and mixing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, persulfate and organic pollutant in the water body to perform oxidative degradation reaction, so as to remove the organic pollutant in the water body.
By the application, the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to the organic pollutants in the 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.
In the application, the initial pH value of the organic pollutant water body is 2-11; the oxidative degradation reaction is carried out at a 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 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, the atomic percentage of the nitrogen in the ordered porous biochar is 7.1% -8.7%, the atomic percentage of the sulfur is 0.4% -1.0%, and the atomic percentage of the phosphorus is 0.1% -1.0%. Compared with the conventional porous biochar, the ordered porous biochar adopted in 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 more quickly and efficiently, a faster mass transfer rate can be obtained, more catalytic sites can be provided, and at the same time, electrons can be transferred more quickly and efficiently; on the basis, a proper amount of sulfur and phosphorus are co-doped into the original nitrogen-doped porous biochar, interaction of low-electronegativity phosphorus and near-electronegativity sulfur with high-electronegativity nitrogen (compared with electronegativity of carbon) can be realized through bonding, induction and the like, the electron distribution condition of the porous biochar is regulated, the surface of the biochar is further induced to form a micro-electric field, the number of surface catalytic sites is enriched, and meanwhile, the graphitization degree of the biochar can be further improved by doped phosphorus, so that the catalytic performance of the biochar is cooperatively improved. However, when the doped sulfur and phosphorus are excessive, the excessive sulfur and phosphorus can break the balance of electron distribution in the biochar carbon skeleton, the doped sulfur and phosphorus mainly exist in the form of oxide, and the excessive oxygen-containing functional groups can reduce the electron transfer effect between the biochar carbon skeleton and the oxidant through steric hindrance and other effects, so that the catalytic activity is reduced, and meanwhile, when the doped sulfur and phosphorus are less, the synergistic promotion effect brought by the sulfur and the phosphorus is weaker, and the catalytic performance of the original nitrogen-doped porous biochar is difficult to improve. 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, environment friendliness and the like, can be used as an activator for activating persulfate, and can effectively remove organic pollutants in water body 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 takes shrimp shells, sulfur sources and triphenylphosphine as raw materials, and prepares 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 through high-temperature cracking calcination and acid modification. In the invention, the shrimp shell is urban organic solid waste, and the shrimp shell is converted into the biochar functional material, so that the waste disposal treatment is realized, and the prepared biochar functional material can be used for environmental pollution treatment, thereby being a win-win strategy. Meanwhile, the shrimp shell is taken as a raw material, and the shrimp shell contains rich nitrogen sources, so that the nitrogen-doped ordered porous biochar can be obtained without adding additional nitrogen sources. On the basis, shrimp shells, sulfur sources and triphenylphosphine are mixed for carbonization, so that sulfur and phosphorus can be successfully doped into the obtained biochar material respectively, the biochar material contains abundant benzene ring structures, the graphitization degree of the doped material can be effectively improved after co-doping, and the electron transfer capacity and the catalytic performance of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar are cooperatively improved. In addition, the acid modification can remove substances such as calcium carbonate and the like which are originally in the shrimp shell biochar, and endow the shrimp shell biochar with rich macroporous, mesoporous and mesoporous structures. More importantly, the phosphorus doping based on triphenylphosphine can induce macropores in the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to be in an ordered trend, so that macropores penetrate through the whole ordered porous biochar 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 nitrogen-sulfur-phosphorus co-doped ordered porous biochar can be improved, a more ordered porous hierarchical structure, a larger specific surface area, more abundant surface oxygen-containing functional groups and more enhanced catalytic capability are finally obtained, and further the nitrogen-sulfur-phosphorus co-doped ordered porous biochar can efficiently activate persulfates, can realize the efficient removal of organic pollutants in a water body in more time, has the performance remarkably superior to that of the undoped biochar, and has a good application prospect in the restoration of the water body polluted by 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 the application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is firstly applied to a high-grade oxidation system of the persulfate, and the direct electron transfer and the singlet oxygen leading are adopted 1 O 2 ) Is supplemented with superoxide anion radical (O) 2 · - ) The dominant free radical path can rapidly and effectively degrade 2, 4-dichlorophenol in the water body, 99% of 2, 4-dichlorophenol (the initial concentration is 100 mg/L) can be removed within 30min of reaction, and the method has the advantages of strong adsorption synergistic catalysis capability, high degradation efficiency, high degradation rate, high pH tolerance and the like, and has obvious advantages in removing organic pollutants in the water body. Meanwhile, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar mainly contains C, H, O, N, S, P and other six elements, 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 recycling, and is a novel catalytic material which has excellent catalytic performance and is environment-friendly and used for activating persulfate and can be widely applied.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying 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-phosphorus co-doped ordered porous biochar (b, c) prepared in example 1 of the present invention.
FIG. 2 is a graph showing the isothermal adsorption and desorption of nitrogen from undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention.
FIG. 3 is a graph showing pore size distribution of undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention.
FIG. 4 is a peak-split diagram of N1s element of undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention.
FIG. 5 is a graph showing the time-removal rate relationship of the persulfate activated by the different activating materials in example 4 of the present invention for removing 2, 4-dichlorophenol in a water body.
FIG. 6 is a graph showing the degradation effect of the activated persulfate on 2, 4-dichlorophenol under different pH conditions of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 5 of the present invention.
FIG. 7 is a graph showing the degradation effect of nitrogen-sulfur-phosphorus co-doped ordered porous biochar activated persulfate with different addition amounts on 2, 4-dichlorophenol in example 6 of the invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
The materials and instruments used in the examples below were all commercially available and the starting materials were analytically pure. In the following examples, the data obtained are all average values of three or more repeated tests unless otherwise specified.
Example 1:
a nitrogen-sulfur-phosphorus co-doped ordered porous biochar comprises ordered porous biochar, wherein the ordered porous biochar is doped with nitrogen, sulfur and phosphorus, the atomic percentage of nitrogen in the ordered porous biochar is 7.42%, the atomic percentage of sulfur is 0.47%, and the atomic percentage of phosphorus is 0.48%.
In this embodiment, the ordered porous biochar contains three pore structures of macropores, mesopores and micropores, wherein the macropores are in an ordered trend and penetrate through the whole ordered biocharPore biochar with pore size of 0.2-0.8 microns, mesoporous with pore size of 2-8 nm and microporous with pore size of 0.5-2 nm. The specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is 971.3m 2 /g。
In the embodiment, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is prepared by taking shrimp shells, sulfur sources and triphenylphosphine as raw materials through high-temperature cracking and calcining (carbonization) and acid modification, and mainly comprises elements such as carbon, oxygen, nitrogen, sulfur, phosphorus and the like.
The preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of the embodiment comprises the following steps:
(1) Doping pretreatment of waste shrimp shells: drying, crushing and sieving the waste shrimp shells with 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 and mixed, followed by grinding treatment to obtain a waste shrimp shell powder (mixed powder) subjected to pretreatment.
(2) Preparation of shrimp shell biochar: and (3) respectively placing the undoped 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 for 2 hours at constant temperature, and taking out after natural cooling to obtain undoped pretreated shrimp shell biochar and doped pretreated shrimp shell biochar.
(3) Modification of shrimp shell biochar: respectively taking 1g of undoped pretreated shrimp shell biochar and doped pretreated shrimp shell biochar prepared in the step (2), respectively adding the undoped pretreated shrimp shell biochar and the doped shrimp shell biochar into 40mL 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), and then stirring at room temperature and under the condition of 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 matters obtained by filtering with deionized water until the solid matters are neutral, and drying the solid matters at 80 ℃ for 24 hours (drying the solid matters at 70-100 ℃ for 18-26 hours) to respectively obtain undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar.
The undoped modified shrimp shell biochar prepared in example 1 and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar were subjected to transmission electron microscopy imaging, 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-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 fully carbonized to biochar; compared with undoped modified shrimp shell biochar, the ordered porous biochar doped with nitrogen, sulfur and phosphorus has obvious pore structure, similar and even macroporous size, obvious ordered trend, and the whole biochar body is penetrated, the pore diameter of macropores is distributed at 0.2-0.8 mu m, the pore diameter of mesopores is distributed at 2-8 nm, and the pore diameter of micropores is distributed at 0.5-2 nm. In addition, as can be seen from fig. 1, the ordered porous biochar co-doped with nitrogen, sulfur and phosphorus by doping modification has obvious graphite stripes, which shows that the graphitization degree is high.
The undoped modified shrimp shell biochar prepared in example 1 and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar were subjected to nitrogen adsorption and desorption characterization, as shown in fig. 2. FIG. 2 is a graph showing the isothermal adsorption and desorption of nitrogen from undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention. FIG. 3 is a graph showing pore size distribution of undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention. As can be seen from FIGS. 2 and 3, compared with undoped modified shrimp shell biochar, the porous structure of the ordered porous biochar co-doped with nitrogen, sulfur and phosphorus is obviously increased, and the specific surface area is 543.6m 2 /g is increased to 971.6m 2 And/g, the number of micropores and mesopores is obviously improved; as can be seen from the combination of ordered macropores in FIG. 1, 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 undoped modified shrimp shell biochar prepared in example 1, 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 and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention. As can be seen from Table 1, the undoped modified shrimp shell biochar contains carbon, oxygen and nitrogen, and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar contains three elements of carbon, oxygen and nitrogen, and two elements of sulfur and phosphorus are added, which indicates that the sulfur and the phosphorus are successfully doped, and the prepared biochar is the nitrogen-sulfur-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 percent of each element in undoped modified shrimp shell biochar and nitrogen sulfur 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 that no detection was made.
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-splitting characterization (X-ray photoelectron spectroscopy), as shown in FIG. 4. FIG. 4 is a peak-split diagram of N1s element of undoped modified shrimp shell biochar and nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in example 1 of the present invention. As can be seen from fig. 4, in the undoped modified shrimp shell biochar and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, three existing forms of pyridine nitrogen (398.3 eV), pyrrole nitrogen (400.2 eV) and graphite nitrogen (401.8 eV) exist in the nitrogen element. Furthermore, as can be seen from fig. 4, compared with undoped modified shrimp shell biochar, the peak of graphite nitrogen (401.8 eV) in the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of the present invention is enhanced, indicating that the graphitization degree is increased; at the same time, a peak belonging to nitrogen oxides (403.2 eV) is added, which shows that the surface of the catalyst contains more oxygen-containing functional groups.
As shown by the test data, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared by the method 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 and the like, is a novel catalytic material which can be widely applied, has excellent catalytic performance, is environment-friendly and is used for activating persulfate, and has more advantages in activating persulfate and degrading and removing organic pollutants in water.
Example 2:
an ordered porous biochar co-doped with nitrogen, sulfur and phosphorus, substantially identical to the ordered porous biochar co-doped with nitrogen, sulfur and phosphorus of example 1, except that: example 2 the atomic percent of nitrogen in the nitrogen-sulfur-phosphorus co-doped ordered porous biochar was 7.87Percent of sulfur is 0.45 percent and percent of phosphorus is 0.13 percent; the specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 2 was 632.3m 2 /g。
The preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of the above embodiment is basically the same as that of embodiment 1, except that: in step (1) of the preparation method of example 2, triphenylphosphine was used in an amount of 0.25g.
Example 3:
an ordered porous biochar co-doped with nitrogen, sulfur and phosphorus, substantially identical to the ordered porous biochar co-doped with nitrogen, sulfur and phosphorus of example 1, except that: example 3 nitrogen sulfur phosphorus co-doped ordered porous biochar with nitrogen at 7.37 atomic percent, sulfur at 0.44 atomic percent and phosphorus at 0.92 atomic percent; example 3 specific surface area of Nitrogen-Sulfur-phosphorus co-doped ordered porous biochar is 1215.3m 2 /g。
The preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of the above embodiment is basically the same as that of embodiment 1, except that: example 3 in step (1) of the preparation process, triphenylphosphine was used in an amount of 1g.
Comparative example 1:
a nitrogen-sulfur co-doped ordered porous biochar substantially identical to the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 1 except that: comparative example 1 nitrogen and sulfur co-doped ordered porous biochar has nitrogen atom percentage of 7.44% and sulfur atom percentage of 0.60%; comparative example 1 Nitrogen-sulfur Co-doped ordered porous biochar has a specific surface area of 550.7m 2 /g。
The preparation method of the nitrogen-sulfur co-doped ordered porous biochar of the above comparative example 1 is basically the same as that of example 1, except that: in the step (1) of the production method of comparative example 1, triphenylphosphine was not added.
Comparative example 2:
a nitrogen-phosphorus co-doped ordered porous biochar substantially identical to the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 1 except that: for a pair of2, the nitrogen and phosphorus co-doped ordered porous biochar has the atomic percent of nitrogen of 7.56 percent and the atomic percent of phosphorus of 0.24 percent; comparative example 2 Nitrogen-phosphorus co-doped ordered porous biochar having a specific surface area of 783.1m 2 /g。
The preparation method of the nitrogen-phosphorus co-doped ordered porous biochar of the above embodiment is basically the same as that of embodiment 1, except that: in the step (1) of the preparation method of comparative example 2, 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 is specifically as follows: the method for degrading the 2, 4-dichlorophenol in the water body by utilizing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to activate sodium persulfate comprises the following steps of:
according to the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution being 2.5:1 and the mass ratio of the persulfate to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution being 10:1, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar and the persulfate prepared in the example 1 are added into the 2, 4-dichlorophenol solution (pH=5.98) with the initial concentration of 100mg/L, oxidative degradation is carried out for 30min at 160rpm and 25 ℃, solid-liquid separation is carried out after the reaction is completed, and the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is recovered.
In this example, the concentration of 2, 4-dichlorophenol was measured by sampling at 0min, 2min, 5min, 10min, 20min, 30min, and the effect of different times on the removal effect of 2, 4-dichlorophenol was calculated.
For comparison effect, undoped treated shrimp shell biochar prepared in example 1, nitrogen-sulfur-phosphorus co-doped ordered porous biochar prepared in examples 2 to 3, nitrogen-sulfur co-doped ordered porous biochar prepared in comparative example 1, nitrogen-phosphorus co-doped ordered porous biochar in comparative example 2 were used to activate persulfate to remove 2, 4-dichlorophenol in water body according to the above steps, and catalytic degradation effect thereof was calculated, and the result is shown in fig. 5.
FIG. 5 is a graph showing the time-removal rate relationship of the persulfate activated by the different activating materials in example 4 of the present invention for removing 2, 4-dichlorophenol in a water body. In fig. 5, a is undoped modified shrimp shell biochar in example 1, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 78.9%, b is ordered porous biochar co-doped with nitrogen, sulfur and phosphorus in example 1, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 99.3%, c is ordered porous biochar co-doped with nitrogen, sulfur and phosphorus in example 2, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 92.8%, d is ordered porous biochar co-doped with nitrogen, sulfur and phosphorus in example 3, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 88.9%, e is ordered porous biochar co-doped with nitrogen and sulfur in comparative example 1, the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 45.6%, f is ordered porous biochar co-doped with nitrogen and phosphorus in comparative example 2, and the removal rate of 2, 4-dichlorophenol after 30min of oxidative degradation is 82.3%. As can be seen from fig. 5, the nitrogen-phosphorus co-doped ordered porous biochar of examples 1 and 2 has significantly improved ability to activate persulfate to degrade 2, 4-dichlorophenol as compared with undoped modified shrimp shell biochar, and the catalytic ability increases with increasing co-doping amount. Compared with undoped modified shrimp shell biochar, the nitrogen-sulfur co-doped ordered porous biochar in comparative example 1 has obviously reduced catalytic degradation capability, and the nitrogen-phosphorus co-doped ordered porous biochar in comparative example 2 has slightly improved catalytic performance. The result shows that the catalytic performance of undoped modified shrimp shell biochar can not be obviously improved by nitrogen-sulfur doping or nitrogen-phosphorus doping, and the excellent performance of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is derived from the synergistic promotion effect among various doping elements of nitrogen, phosphorus and sulfur. Therefore, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar activated persulfate prepared by the method 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 is specifically as follows: the method for degrading the 2, 4-dichlorophenol in the water body by utilizing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to activate sodium persulfate comprises the following steps of:
according to the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution being 2.5:1 and the mass ratio of the persulfate to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution being 10:1, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar and the persulfate in the example 1 are respectively added into the 2, 4-dichlorophenol solution (the initial concentration of the solution is 100 mg/L) with pH values of 2.14, 3.95, 5.98, 8.02 and 10.35, and oxidative degradation is carried out for 30min at 160rpm and 25 ℃, solid-liquid separation is carried out after the reaction is completed, and the nitrogen-sulfur-phosphorus co-doped 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, and the effect of different times on the removal effect of 2, 4-dichlorophenol was calculated, and the results are shown in FIG. 6.
FIG. 6 is a graph showing the degradation effect of the activated persulfate on 2, 4-dichlorophenol under different pH conditions of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar of example 5 of the present invention. As can be seen from FIG. 6, the removal rates of 2, 4-dichlorophenol at pH values of 2.14, 3.95, 5.98, 8.02 and 10.35 were 94.1%, 98.5%, 99.3%, 98.2% and 98.7%, respectively. Therefore, when the persulfate is activated by utilizing the ordered porous biochar co-doped with nitrogen, sulfur and phosphorus to degrade organic pollutants, the method can not only rapidly and efficiently degrade 2, 4-dichlorophenol under acidic and weak acidic conditions, but also rapidly degrade 2, 4-dichlorophenol under alkaline conditions, thereby realizing the effective and rapid degradation of 2, 4-dichlorophenol, and having good application prospects in the actual treatment of 2, 4-dichlorophenol wastewater.
Example 6:
the application of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate is specifically as follows: the method for degrading the 2, 4-dichlorophenol in the water body by utilizing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to activate sodium persulfate comprises the following steps of:
according to the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution being 0:1, 1.5:1, 2.5:1 and 3.5:1, the mass ratio of the persulfate to the 2, 4-dichlorophenol in the 2, 4-dichlorophenol solution being 10:1, the nitrogen-sulfur-phosphorus co-doped ordered porous biochar and the persulfate in the embodiment 1 are respectively added into the 2, 4-dichlorophenol solution with the initial concentration of 100mg/L, oxidative degradation is carried out for 30min at 160rpm and 25 ℃, solid-liquid separation is carried out after the reaction is completed, and the nitrogen-sulfur-phosphorus co-doped 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, and the effect of different times on the removal effect of 2, 4-dichlorophenol was calculated, and the results are shown in FIG. 7.
FIG. 7 is a graph showing the degradation effect of nitrogen-sulfur-phosphorus co-doped ordered porous biochar activated persulfate with different addition amounts on 2, 4-dichlorophenol in example 6 of the invention. As can be seen from fig. 7, when only persulfate is used in the system and the ordered porous biochar is not co-doped with nitrogen, sulfur and phosphorus, the 2, 4-dichlorophenol is hardly degraded; however, when adding the nitrogen-sulfur-phosphorus co-doped ordered porous biochar into the system, the 2, 4-dichlorophenol is rapidly oxidized and degraded, and the removal rate of the system to the 2, 4-dichlorophenol increases with the added amount of the added ordered porous biochar until 100% is removed; 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 result shows that 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, environment friendliness and the like, can be used as an activator for activating persulfate, and can effectively remove organic pollutants in water body by effectively activating persulfate, so that the nitrogen-sulfur-phosphorus co-doped ordered porous biochar has high use value and good application prospect.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (5)
1. An application of nitrogen-sulfur-phosphorus co-doped ordered porous biochar in removing organic pollutants in water by activating persulfate, which comprises the following steps: mixing the nitrogen-sulfur-phosphorus co-doped ordered porous biochar, persulfate and organic pollutant water body to perform oxidative degradation reaction, so as to remove organic pollutants in the water body; the mass ratio of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar to the organic pollutants in the organic pollutant water body is 2.5-5:1; 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;
the preparation method of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar comprises the following steps of:
s1, mixing shrimp shells, sulfur sources and triphenylphosphine, and grinding to obtain mixed powder; the mass ratio of the triphenylphosphine to the shrimp shell is 0.5:1; the mass ratio of the sulfur source to the shrimp shell is 0.25:1;
s2, carbonizing the mixed powder obtained in the step S1 to obtain a shrimp shell biochar material;
s3, carrying out acid modification on the shrimp shell biochar material obtained in the step S2 to obtain the nitrogen-sulfur-phosphorus co-doped ordered porous biochar;
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 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%.
2. The use according to claim 1, wherein the initial pH of the body of organic contaminant water is from 2 to 11; the oxidative degradation reaction is carried out at a 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.
3. The use according to claim 1, wherein in step S1, the sulfur source is bisphenol S.
4. A use according to claim 1 or 3, wherein in step S1 the shrimp shell further comprises the following treatments prior to use: drying shrimp shell, pulverizing, sieving, and making into shrimp shell powder;
in the step S2, the carbonization is carried out under the protection of inert atmosphere; the heating rate in the carbonization process is 5-10 ℃/min; the carbonization temperature is 700-900 ℃; the carbonization time is 1 h-3 h;
in the step S3, the acid modification is carried out by mixing shrimp shell biochar material with acid solution, ultrasonic dispersing and stirring; 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 hydrochloric acid solution or sulfuric acid solution; the concentration of the acid solution is 1 mol/L-2 mol/L; the ultrasonic dispersion time is 5-25 min; the rotation speed of the stirring is 300 rpm-650 rpm; the stirring time is 2h.
5. The use according to claim 1, wherein the ordered porous biochar comprises three pore structures of macropores, mesopores and micropores, the macropores being in an ordered orientation and extending throughout the ordered porous biochar; the pore diameter of the macropores is distributed between 0.2 and 0.8 mu m; the pore diameter of the mesoporous is distributed between 2nm and 8nm; the pore diameter of the micropores is distributed between 0.5 and nm and 2nm; the specific surface area of the nitrogen-sulfur-phosphorus co-doped ordered porous biochar is 600m 2 /g～1000 m 2 /g。
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