阅读说明：本技术 一种氮磷硫共掺杂多孔碳负载的金属磷化物纳米复合材料及其制备方法与应用 (Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof ) 是由 李萍 林于楠 陈冉 李文琴 于 2020-05-08 设计创作，主要内容包括：本发明公开了一种氮磷硫共掺杂多孔碳负载的金属磷化物纳米复合材料及其制备方法与应用。所述材料的制备步骤为：S1.将金属盐、碳源化合物及膨化剂均匀混合后,在惰性气体氛围下热解,得到M-g-C<Sub>3</Sub>N<Sub>4</Sub>；S2.将所述M-g-C<Sub>3</Sub>N<Sub>4</Sub>分散于溶剂中,得到悬浮液A,然后将溶有六氯环三磷腈和4,4-二羟基二苯砜的混合溶液B滴加至悬浮液A中,混合反应；然后再滴加碱性辅剂,混匀反应,待反应结束后,分离得到M-g-C<Sub>3</Sub>N<Sub>4</Sub>@PZS；S3.将所述M-g-C<Sub>3</Sub>N<Sub>4</Sub>@PZS在惰性气体氛围下,高温热解,得到所述氮磷硫共掺杂多孔碳负载的金属磷化物纳米复合材料MP<Sub>x</Sub>-NPS-C。所述材料的制备简单、普遍适用性高；且制备的材料在催化活化H<Sub>2</Sub>O<Sub>2</Sub>、PMS、PS降解复杂有机化合物中表现出优异的性能,拓宽了金属磷化物材料在高级氧化水处理中的应用。(The invention discloses a nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nano composite material as well as a preparation method and application thereof. The preparation steps of the material are as follows: s1, uniformly mixing metal salt, a carbon source compound and a swelling agent, and pyrolyzing in an inert gas atmosphere to obtain M-g-C 3 N 4 (ii) a S2, mixing the M-g-C 3 N 4 Dispersing in a solvent to obtain a suspension A, then dropwise adding a mixed solution B dissolved with hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone into the suspension A, and carrying out mixed reaction;then dripping alkaline auxiliary agent, mixing uniformly and reacting, and separating to obtain M-g-C after reaction 3 N 4 @ PZS; s3, mixing the M-g-C 3 N 4 The @ PZS is pyrolyzed at high temperature in the inert gas atmosphere to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite MP x -NPS-C. The material is simple to prepare and high in general applicability; and the prepared material is subjected to catalytic activation H 2 O 2 PMS and PS show excellent performance in degrading complex organic compounds, and broaden the application of metal phosphide materials in advanced oxidation water treatment.)

1. The preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite is characterized by comprising the following steps:

s1, uniformly mixing metal salt, a carbon source compound and a swelling agent, and pyrolyzing in an inert gas atmosphere to obtain M-g-C₃N₄；

S2, mixing the M-g-C₃N₄Dispersing in a solvent to obtain a suspension A, then dropwise adding a mixed solution B dissolved with hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone into the suspension A, and carrying out mixed reaction; then dripping alkaline auxiliary agent, mixing uniformly and reacting, and separating to obtain M-g-C after reaction₃N₄@PZS；

S3, mixing the M-g-C₃N₄The @ PZS is pyrolyzed at high temperature in the inert gas atmosphere to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite MP_x-NPS-C。

2. The method for preparing the nitrogen-phosphorus-sulfur co-doped porous carbon-supported metal phosphide nanocomposite material according to claim 1, wherein the metal salt in the step S1 is at least one of metal acetate, metal nitrate, metal sulfate, metal carbonate and metal chloride.

3. The preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded metal phosphide nanocomposite material according to claim 1, wherein the carbon source compound is at least one of melamine, dicyandiamide, cyanamide, urea, glucose, maltose, sugar alcohol, sucrose, starch, cellulose, lignin, citric acid, epoxy resin, phenolic resin, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile or carbon black

The swelling agent is at least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate or sodium bicarbonate.

4. The preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded metal phosphide nanocomposite material as claimed in claim 1, wherein the pyrolysis temperature in the step S1 is 400-650 ℃, and the pyrolysis time is 1-20 h.

5. The preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded metal phosphide nanocomposite material as claimed in claim 1, wherein the dropping speed of the mixed solution B in the step S2 is 20-100 mL/h.

6. The method for preparing the nitrogen-phosphorus-sulfur co-doped porous carbon-supported metal phosphide nanocomposite material according to claim 1, wherein the basic auxiliary agent is at least one of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, aniline, p-toluidine, p-nitroaniline, diphenylamine, benzylamine, sodium hydroxide, potassium hydroxide, magnesium hydroxide, aluminum hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia water, pyridine, dimethylimidazole, benzimidazole, 2-hydroxybenzimidazole, 1-n-butylimidazole or 4-nitroimidazole. The dropping speed of the alkaline auxiliary agent is 5-50 mL/h.

7. The preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded metal phosphide nanocomposite material as claimed in claim 1, wherein M-g-C in the mixed solution B is mixed with the suspension A₃N₄The amount of HCCP is 1: 0-40, wherein HCCP is not 0.

8. The preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded metal phosphide nanocomposite material according to claim 1, wherein in the step S3, the pyrolysis temperature is 700-1200 ℃; the pyrolysis time is 1-20 h.

9. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite prepared by the method of any one of claims 1 to 8.

10. The application of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite material disclosed by claim 9 as an electro-catalytic hydrogen evolution, electro-catalytic water cracking, photo-catalytic water cracking or Fenton advanced oxidation catalyst(s).

Technical Field

The invention relates to the technical field of water pollution treatment, in particular to a nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nano composite material and a preparation method and application thereof.

Background

With the continuous flourishing development of the urban chemical industry and the like, the industrial wastewater pollution gradually becomes a global environmental problem. The industrial wastewater has complex components, wherein the organic matters which are difficult to degrade have complex molecular structures and strong chemical stability, which can cause persistent pollution, and the traditional municipal sewage biochemical treatment system can not achieve the effect of complete purification. Therefore, the search for a more effective water treatment method has profound significance for relieving the current water environment pollution problem. In a plurality of emerging water treatment processes, the Fenton (like) technology has wide application prospect in treating complex organic matters in water.

The Fenton advanced oxidation technology comprises two main types of homogeneous systems and heterogeneous systems. Compared with the homogeneous Fenton method (similar Fenton method), the heterogeneous method has the following advantages: (1) after the reaction, the heterogeneous catalyst, especially the ferromagnetic material is easy to separate and recover from the system; (2) most heterogeneous catalysts have strong chemical stability, can be recycled and even can be regenerated, and have high material utilization rate; (3) the metal in the heterogeneous system is dissolved out less, and the water environment is not affected generally; (4) heterogeneous catalysts are various in types, controllable in morphology and structure and various in preparation method, and development and application of the technical field of Fenton advanced oxidation (like) are enriched and widened. Therefore, the heterogeneous Fenton method has great practical popularization potential, and increasingly attracts close attention and research of people.

At present, the research on heterogeneous catalysts mainly focuses on the aspects of nano zero-valent iron, ferrite, metal oxide and the like, and the research on metal phosphide-based materials in advanced oxidation is rarely reported. In recent years, the metal phosphide is found to show excellent performance in Fenton advanced oxidation (like), and is a very potential catalyst. However, the existing metal phosphide material still faces the problems of low catalytic activity, poor chemical stability, easy particle agglomeration, easy loss of metal ions and the like, and the popularization and practical application of the metal phosphide material are greatly hindered. On the other hand, the microscopic physical structure and surface chemical structure of the material have a decisive influence on the performance, so that the performance of the metal phosphide material can be further improved by rational design and control of the morphology, composition, structure and the like of the metal phosphide material, and the work in this respect is also urgently needed.

Disclosure of Invention

The invention aims to provide a nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite aiming at the defects and defects of the application of metal phosphide as a Fenton advanced oxidation heterogeneous catalyst in the prior art.

The invention also aims to provide a preparation method of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite.

The invention further aims to provide application of the nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nanocomposite.

The above object of the present invention is achieved by the following scheme:

a preparation method of a metal phosphide nanocomposite loaded with nitrogen, phosphorus and sulfur co-doped porous carbon comprises the following steps:

s1, uniformly mixing metal salt, a carbon source compound and a swelling agent, and pyrolyzing in an inert gas atmosphere to obtain M-g-C₃N₄；

S2, mixing the M-g-C₃N₄Dispersing in a solvent to obtain a suspension A, then dropwise adding a mixed solution B dissolved with hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone into the suspension A, and carrying out mixed reaction; then dripping alkaline auxiliary agent, mixing uniformly and reacting, and separating to obtain M-g-C after reaction₃N₄@PZS；

S3, mixing the M-g-C₃N₄The @ PZS is pyrolyzed at high temperature in the gas atmosphere to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite MP_x-NPS-C。

The invention obtains the nano composite material with high catalytic activity and stability by loading the high-dispersion ultrafine metal phosphide nano particles on the multi-doped carbon porous nano sheet, and when the nano composite material is used as a catalyst, the nano composite material has the following advantages: 1) the high specific surface area and the porous structure of the carbon material and the superfine size of the metal phosphide nano particles ensure that the composite catalyst material can fully expose reaction active sites; 2) the porous ultrathin nanosheet structure is beneficial to mass transfer diffusion; 3) the multi-doped carbon porous nanosheet can highly disperse metal phosphide, prevent metal loss and nanoparticle agglomeration, improve the stability of the material and facilitate recycling; 4) the heteroatom co-doping can provide more active sites for the material and improve the catalytic activity; 5) the carbon material is green and pollution-free, and has certain catalytic performance.

Preferably, the metal salt in step S1 is at least one of metal acetate, metal nitrate, metal sulfate, metal carbonate, or metal chloride.

Preferably, the metal in the metal salt in step S1 is at least one of (transition metal) Mn, Fe, Co, Cu, Ni, Ce, Cr, Zn, V, Ti, Sc, Mo, W, Cd, Zr, Nb, Tc, Bh, (rare earth metal) Lu, Ce, Pr, Tb, Y, Sc, (noble metal) Pd, Ru, Rh, Pt, Ir, Os, Au or Ag.

Preferably, the carbon source compound is at least one of melamine, dicyandiamide, cyanamide, urea, glucose, maltose, sugar alcohol, sucrose, starch, cellulose, lignin, citric acid, epoxy resin, phenol resin, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, or carbon black.

The bulking machine is at least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate or sodium bicarbonate.

Preferably, in the step S1, the temperature rise rate of the pyrolysis is 1-50 ℃/min; preferably 1-30 ℃/min; more preferably 2 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, 2-5 ℃/min, 5-10 ℃/min, 5-15 ℃/min, 10-20 ℃/min, 5-20 ℃/min, 15-20 ℃/min, 2-10 ℃/min, 2-15 ℃/min or 2-20 ℃/min.

Preferably, in step S1, the pyrolysis temperature is 400-650 ℃; preferably 450 to 600 ℃; more preferably 480 ℃, 500 ℃, 550 ℃, 580 ℃, 480-500 ℃, 500-550 ℃, 550-580 ℃, 480-550 ℃, 480-580 ℃ or 500-580 ℃. The carbon source used in the temperature range can be decomposed and converted into g-C₃N₄The metal salt is converted into metal-based nano particles loaded on the metal-based nano particles to generate M-g-C₃N₄A material.

Preferably, in the step S1, the pyrolysis time is 1-20 h; preferably 2-16 h; more preferably 2 hours, 5 hours, 10 hours, 15 hours, 2 to 5 hours, 2 to 10 hours, 3 to 4 hours, 2 to 15 hours, 5 to 10 hours, 5 to 15 hours or 10 to 15 hours. Enough pyrolysis time ensures that the metal salt and the carbon source are fully decomposed and completely converted into M-g-C₃N₄. However, too long a pyrolysis time may lead to excessive agglomeration problems of the metal-based nanoparticles. Thus requiring a suitable pyrolysis time frame. Preferably, in step S1, the metal salt, the carbon source compound, and the swelling agent are first mixed in water, and then heated to remove water, so as to obtain a uniformly mixed powder; or grinding the metal salt, the carbon source compound and the swelling agent into powder and then uniformly mixing to obtain mixed powder.

Preferably, in step S1, the ratio of the metal salt, the carbon source compound and the swelling agent may be 1: 10-100: 0-500; more preferably, the ratio is 1: 24: 100-200, 1: 30: 130-240, 1: 40: 180-310 or 1: 60: 270-470.

Preferably, in step S1, the cooling mode after pyrolysis is natural cooling or program forced cooling.

Preferably, in step S1, the inert gas is nitrogen (N)₂) At least one of argon (Ar) or helium (He).

Preferably, in step S2, the basic auxiliary agent is at least one of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, aniline, p-toluidine, p-nitroaniline, diphenylamine, benzylamine, sodium hydroxide, potassium hydroxide, magnesium hydroxide, aluminum hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, pyridine, dimethylimidazole, benzimidazole, 2-hydroxybenzimidazole, 1-n-butylimidazole or 4-nitroimidazole.

Preferably, in step S2, the solvent may be at least one of methanol, ethanol, propanol, butanol, isopropanol, ethylene glycol, propylene glycol, 1, 4-butanediol, 1,2, 4-butanetriol, 1, 6-hexanediol, pentanediol, glycerol, benzyl alcohol, cycloethanol, acetone, diethylene glycol, triethylene glycol, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, methyl acetate, ethyl acetate, dimethyl sulfoxide, dimethylformamide, or deionized water.

Preferably, in step S2, the solvent in the mixed solution B is the same as the solvent in the suspension a.

Preferably, in step S2, M-g-C in the suspension A₃N₄The mass volume ratio of the solvent to the solvent is (0.01-30): 1000, specifically (0.1-25): 1000; more specifically (0.1-5: 1000), (5-10: 1000), (0.1-10: 1000, (0.1-20: 1000), (10-20: 1000 or (5-20: 1000).

Preferably, in step S2, after the mixed solution B is mixed with the suspension A, M-g-C in the solution₃N₄The substance amount ratio to HCCP is 1: 0-40, specifically 1: 0-10, 1: 0-20, 1: 0-30, 1: 10-20, 1: 20-30 or 1: 10-30, wherein HCCP is not 0.

Preferably, in step S2, the mass-to-volume ratio of the HCCP, the BPS, and the solvent in the mixed solution B is 0.2: 0.1-10: 10-10000, and more particularly 0.2: 0.3-8: 50-8000.

Preferably, in the step S2, the dropping speed of the mixed solution B is 20-100 mL/h. The dropping speed cannot be too fast to form a uniform system, which is beneficial to the uniform coating of the subsequent PZS.

Preferably, in step S2, the mixing time of the mixed solution B and the suspension a is 10-60 min; more preferably 15 to 30min, more preferably 15min, 18min, 20min, 24min, 15 to 18min, 15 to 20min, 15 to 24min, 18 to 20min, 20 to 24 min.

Preferably, in step S2, the mass-to-volume ratio of the HCCP to the basic auxiliary agent is (0.01-2): 1; preferably (0.05-1): 1; more preferably (0.1-0.3): 1, (0.1-0.5): 1, (0.1-0.8): 1, (0.3-0.5): 1, (0.3-0.8): 1 or (0.5-0.8): 1.

Preferably, in step S2, the dropping speed of the basic auxiliary agent is 5 to 50 mL/h. The speed is slow enough to ensure that the PZS is at M-g-C₃N₄The material surface is uniformly formed.

Preferably, in the step S2, the reaction time after the alkaline auxiliary agent is dripped is 5-48 h; preferably 6 to 36 hours, more preferably 6 hours, 8 hours, 10 hours, 12 hours, 24 hours, 6 to 16 hours, 6 to 8 hours, 8 to 10 hours, 6 to 10 hours, 10 to 12 hours, 8 to 12 hours, 6 to 12 hours, 12 to 24 hours, 10 to 24 hours, 8 to 24 hours or 6 to 24 hours.

Preferably, the separation process after the reaction in step S2 is: naturally settling, filtering or centrifuging the reaction solution to obtain a solid substance, washing and drying to obtain M-g-C₃N₄@PZS。

More preferably, the washing is performed using at least one solvent of methanol, ethanol, or acetonitrile.

More preferably, the drying condition can be set to be 30-150 ℃ for 3-48 h.

Preferably, in the step S3, the temperature rise rate in the pyrolysis process is 1 to 50 ℃/min; preferably 1-30 ℃/min; more preferably 2 ℃/min, 5 ℃/min, 10 ℃/min, 30 ℃/min, 2-5 ℃/min, 2-10 ℃/min, 2-30 ℃/min, 5-10 ℃/min or 10-30 ℃/min.

Preferably, in step S3, the temperature of the pyrolysis process is 700-1200 ℃; preferably 800-1100 ℃; more preferably 800 deg.C, 850 deg.C, 900 deg.C, 1000 deg.C, 8 deg.C00-850 ℃, 850-900 ℃, 800-900 ℃, 900-1000 ℃, 850-1000 ℃ or 800-1000 ℃. In this temperature range, the PZS can be strongly decomposed, on the one hand, with the M-g-C carbonized at high temperature₃N₄The nitrogen, phosphorus and sulfur co-doped porous carbon is generated together, and on the other hand, P and M-g-C decomposed by the polymer are₃N₄The metal in (1) is combined to form metal phosphide supported on porous carbon.

Preferably, in the step S3, the pyrolysis time is 1-20 h; preferably 1-15 h; furthermore; preferably 1 hour, 5 hours, 8 hours, 15 hours, 1 to 5 hours, 1 to 8 hours, 1 to 15 hours, 5 to 8 hours, 5 to 15 hours or 8 to 15 hours.

Preferably, in step S3, the cooling mode after the pyrolysis reaction is natural cooling or program forced cooling.

Preferably, in step S3, the gas in the pyrolysis process may be an inert gas, or a mixed gas of an inert gas and a reaction gas; preferably, the inert gas may be nitrogen (N)₂) At least one of argon (Ar) or helium (He); preferably, the reaction gas may be ammonia (NH)₃) Hydrogen sulfide (H)₂S) or Phosphine (PH)₃) At least one of (1).

The invention also protects the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nano composite material prepared by the method.

Preferably, the apparent physical form of the nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nanocomposite is porous nanosheet-shaped.

Preferably, the diameter of the nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material is 0.5-10 mu m, the thickness is 2-30 nm, and the material specific surface area is 500-1400 m²g^-1The pore volume is 0.45-1.50 cm³g^-1。

The application of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nanocomposite as an electrochemical catalysis, photochemical catalysis, photocatalytic water cracking or Fenton advanced oxidation catalyst (like) is also in the protection scope of the invention.

Preferably, the electrochemical catalysis comprises an electrocatalytic hydrogen evolution reaction or an electrocatalytic water splitting reaction.

Preferably, the photochemical catalysis comprises a photocatalytic hydrogen evolution reaction or a photocatalytic water splitting reaction.

Preferably, the Fenton-like advanced oxidation comprises Fenton's technique of activating hydrogen peroxide, activating Peroxymonosulfate (PMS) or Persulfate (PS).

Preferably, the nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material is applied to a photoelectricity synergistic catalytic hydrogen evolution reaction, a photoelectricity synergistic catalytic water splitting reaction or a photocatalysis activation PMS synergistic advanced oxidation reaction catalyst.

Preferably, the nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nanocomposite is applied as a biosensor material.

Compared with the prior art, the invention has the following beneficial effects:

the nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nano composite material prepared by the invention has the following advantages: 1) the metal phosphide nano-particles are beneficial to fully exposing reactive sites; 2) the carbon material is used as a carrier, so that the specific surface area and the porosity of the material are greatly improved, and the adsorption of reactants and the contact with active sites are facilitated; 3) the porous carbon material can well disperse metal phosphide nanoparticles, prevent the nanoparticles from agglomerating, inhibit the dissolution of metal ions and improve the stability of the material; 4) the PZS coating provides a phosphorus source for in-situ generation of metal phosphide, other phosphorus sources do not need to be added, and meanwhile, the PZS coating is also a source of N, P, S heteroatom co-doping and can provide more active sites for the nano composite material;

meanwhile, the synthesis method provided by the invention has the advantages of simple operation, rapid reaction, flexible conditions and high general applicability; and the prepared nitrogen-phosphorus-sulfur co-doped porous carbon loaded metal phosphide nano composite material is used for catalyzing and activating H₂O₂PMS and PS show excellent performance in degrading complex organic compounds, and broaden the application of metal phosphide materials in advanced oxidation water treatment.

Drawings

Fig. 1 is an X-ray powder diffraction pattern of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded cobalt phosphide nanocomposite prepared in example 1.

Fig. 2 is an SEM image of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded titanium phosphide nanocomposite prepared in example 2.

Fig. 3 is an SEM image of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded manganese phosphide nanocomposite prepared in example 3.

Fig. 4 is a graph showing the performance of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded cobalt phosphide nanocomposite material prepared in example 1 on PMS degradation activation versus chlorophenol.

Fig. 5 is a performance diagram of degradation of methylene blue by activated PMS of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded manganese phosphide nanocomposite prepared in example 3.

Fig. 6 is an SEM image of the nitrogen, phosphorus and sulfur co-doped porous carbon-loaded cobalt-nickel bimetallic phosphide nanocomposite prepared in example 6.

Fig. 7 is a TEM image of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt-nickel bimetallic phosphide nanocomposite prepared in example 6.

Fig. 8 is an SEM image of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded manganese-vanadium bimetallic phosphide nanocomposite prepared in example 7.

Fig. 9 is a performance diagram of degradation of rhodamine B by activated PS of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded cobalt-nickel phosphide nanocomposite prepared in example 6.

Fig. 10 is a performance diagram of degradation of tetracycline by activated PMS of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded manganese vanadium phosphide nanocomposite prepared in example 7.

Fig. 11 is a TEM image of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded platinum iron copper trimetal phosphide nanocomposite prepared in example 10.

Fig. 12 is an X-ray powder diffraction pattern of the nitrogen-phosphorus-sulfur co-doped porous carbon-supported nickel phosphide nanocomposite prepared in example 11.

Fig. 13 is a performance diagram of degradation of acyclovir by activated PMS of the nitrogen-phosphorus-sulfur co-doped porous carbon-loaded nickel phosphide nanocomposite prepared in example 11.

Fig. 14 is a SEM of the nitrogen, phosphorus and sulfur co-doped porous carbon loaded iron-molybdenum bi-metal phosphide nanocomposite prepared in example 12.

Fig. 15 shows TEM of the nitrogen, phosphorus and sulfur co-doped porous carbon loaded iron-molybdenum bi-metal phosphide nanocomposite prepared in example 12.

FIG. 16 shows activation H of the NPS-codoped porous carbon-loaded Fe-Mo bimetal phosphide nanocomposite prepared in example 12₂O₂Degradation of bisphenol A performance diagram.

Detailed Description

The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.