CN111717902A - Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof - Google Patents
Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof Download PDFInfo
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- CN111717902A CN111717902A CN202010382094.9A CN202010382094A CN111717902A CN 111717902 A CN111717902 A CN 111717902A CN 202010382094 A CN202010382094 A CN 202010382094A CN 111717902 A CN111717902 A CN 111717902A
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- phosphorus
- sulfur
- nitrogen
- porous carbon
- doped porous
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- 229910052757 nitrogen Inorganic materials 0.000 title description 22
- 229910052698 phosphorus Inorganic materials 0.000 title description 19
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- 238000011160 research Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- IUNUQZUNCWXDMP-UHFFFAOYSA-N copper iron platinum Chemical compound [Fe][Pt][Cu] IUNUQZUNCWXDMP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- HUZUGBHWXHUABJ-UHFFFAOYSA-N [Pt].[Fe].[Ti] Chemical compound [Pt].[Fe].[Ti] HUZUGBHWXHUABJ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021475 bohrium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ZTPQLYJGPLYBPS-UHFFFAOYSA-N phosphanylidynechromium Chemical compound [Cr]#P ZTPQLYJGPLYBPS-UHFFFAOYSA-N 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
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-C3N4(ii) a 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 MPx-NPS-C. The material is simple to prepare and high in general applicability; and the prepared material is subjected to catalytic activation H2O2PMS and PS show excellent performance in degrading complex organic compounds, and broaden the application of metal phosphide materials in advanced oxidation water treatment.
Description
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 MPx-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.
Example 1 preparation of cobalt phosphide nanocomposite loaded with nitrogen, phosphorus and sulfur co-doped porous carbon
The preparation process comprises the following steps:
0.0747g (0.3mmol) of cobalt acetate [ Co (CH)3COO)2·4H2O]Heating and refluxing 3g of dicyanodiamine and 15g of ammonium chloride in 30mL of deionized water at 80 ℃ for 4 hours to obtain a completely dissolved mixed solution, heating to 100 ℃ to evaporate the deionized water, and completely drying in a 100 ℃ oven to obtain uniformly mixed powder of the dicyanodiamine, the ammonium chloride and the deionized water; raising the temperature of the mixed powder from room temperature to 550 ℃ at the heating rate of 2 ℃/min in a tubular furnace, carrying out pyrolysis at 550 ℃ for 2h, and introducing N into the tubular furnace2Controlling the flow rate at 20-30mL/min, and naturally cooling to obtain Co-g-C3N4A material;
200mg of Co-g-C3N4Carrying out ultrasonic treatment on the material in 50mL of methanol for 30min to obtain a well-dispersed suspension A; slowly dropwise adding 15mL of methanol solution dissolved with 150mg of HCCP and 350mg of BPS into the suspension A; after mixing for 15-20min, continuously and slowly dripping the mixed solution of 500 mu L triethylamine and 500 mu L methanol, continuously reacting for 12h, and then carrying out separation operation.The suspension was kept stirred during the above process, and the rotation speed was maintained at 650 rpm. The reacted material is filtered by an organic mixed nylon new sub-filtration membrane with the aperture of 0.45 mu m, washed by ethanol for 3 times and dried in a drying oven at 60 ℃ for 6 hours to obtain Co-g-C3N4@ PZS material;
400mg of Co-g-C was taken3N4The @ PZS material is pyrolyzed in a tube furnace, the temperature is raised from room temperature to 800 ℃ at the temperature rise rate of 2 ℃/min, the material stays for 1.5h at the temperature of 800 ℃, and N is introduced into the tube furnace2And controlling the flow rate to be 20-30mL/min, and naturally cooling to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt phosphide nano composite material (CoP-NPS-C).
Characterization of the materials:
the crystal phase of the product is identified to be cobalt phosphide by an X-ray powder diffractometer (as shown in figure 1);
example 2 preparation of Nitrogen, phosphorus and Sulfur codoped porous carbon loaded titanium phosphide nanocomposite
The preparation process comprises the following steps:
24g (100mmol) of titanium sulfate [ Ti (SO) ]4)2]800g of urea and 2kg of ammonium carbonate are ground and mixed to obtain powder which is uniformly mixed with the urea, the ammonium carbonate and the ammonium carbonate; raising the temperature of the mixed powder from room temperature to 580 ℃ at the heating rate of 5 ℃/min in a tubular furnace, pyrolyzing the mixed powder for 4 hours at the temperature of 580 ℃, introducing He into the tubular furnace, controlling the flow rate to be about 50mL/min, and naturally cooling to obtain Ti-g-C3N4A material;
80g of Ti-g-C3N4Ultrasonically treating the material in 4L of ethanol for 45min to obtain a well-dispersed suspension A; dropwise adding 1L of ethanol solution dissolved with 80g of HCCP and 200g of BPS into the suspension A; after mixing for 40min, 400mL of dimethylamine was continuously and slowly added dropwise, and the reaction was continued for 30 hours, followed by separation. In the above process, the suspension was kept in a stirred state at 1000 rpm. Naturally settling the reacted material to remove supernatant, further separating solid phase and liquid phase by centrifugation at 10000rpm for 5min, washing with methanol for 1 time, and drying in an oven at 80 deg.C for 3h to obtain Ti-g-C3N4@ PZS material;
taking 30g of Ti-g-C3N4And (3) pyrolyzing the @ PZS material in a tubular furnace, heating the temperature from room temperature to 900 ℃ at the heating rate of 10 ℃/min, staying at 900 ℃ for 6h, introducing He into the tubular furnace, controlling the flow rate to be about 40mL/min, and naturally cooling to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded chromium phosphide nanocomposite (TiP-NPS-C).
Characterization of the materials:
the morphology was characterized by SEM (as shown in FIG. 2) and was seen to be a porous sheet-like stack structure with a sheet diameter of about 1-4 μm;
example 3 preparation of Nitrogen phosphorus Sulfur codoped porous carbon loaded manganese phosphide nanocomposite
The preparation process comprises the following steps:
12.25g (50mmol) of manganese acetate [ Mn (CH) ]3COO)2·4H2O]Heating and refluxing 100g of melamine and 100g of ammonium sulfate in 1L of deionized water at 60 ℃ for 12h to obtain a completely dissolved mixed solution, heating to 90 ℃ to evaporate the deionized water, completely drying in a 100 ℃ oven, and grinding to obtain uniformly mixed powder of the melamine and the ammonium sulfate; raising the temperature of the mixed powder from room temperature to 650 ℃ at the heating rate of 20 ℃/min in a tubular furnace, pyrolyzing the mixed powder for 2 hours at the temperature of 650 ℃, introducing N2 into the tubular furnace, controlling the flow rate to be 30-40mL/min, and reducing the temperature to the room temperature at the speed of 10 ℃/min to obtain Mn-g-C3N4A material;
5g of Mn-g-C3N4Carrying out ultrasonic treatment on the material in 1L of acetonitrile for 60min to obtain a well-dispersed suspension A; 200mL of acetonitrile solution in which 3g of HCCP and 10g of BPS were dissolved was added to suspension A; after mixing for 40min, continuously and slowly dripping a mixed solution of 40mL aniline and 60mL ethanol, continuously reacting for 24h, and then carrying out separation operation. In the above process, the suspension was kept in a stirred state at 900 rpm. The reacted material is filtered by an organic mixed nylon new sub-filtration membrane with the aperture of 0.45 mu m, washed by ethanol for 5 times and dried in an oven at 80 ℃ for 1h to obtain Mn-g-C3N4@ PZS material;
taking 10g of Mn-g-C3N4The @ PZS material is pyrolyzed in a tube furnace from room temperature to 1000 ℃ at a heating rate of 24 ℃/minStaying at 1000 ℃ for 4 hours, and introducing N into a tube furnace2Controlling the flow rate to be about 30-40mL/min, and reducing the flow rate to room temperature at the rate of 20 ℃/min to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded vanadium phosphide nano composite material (MnP-NPS-C).
Characterization of the materials:
the morphology was characterized by SEM (as shown in FIG. 3) and it can be seen that it exhibited a loose porous sheet stack structure with sheet diameters of about 1-3 μm;
example 4 Performance testing of NPS-codoped porous carbon-loaded cobalt phosphide nanocomposite in advanced oxidation of activated peroxymonosulfate
The catalytic performance of the material prepared in example 1 for activating PMS to degrade parachlorophenol solution was tested using parachlorophenol as a substrate. In the system, the initial concentration of p-chlorophenol is 50mg/L, the initial concentration of the catalyst is 50mg/L, and the initial concentration of PMS is 500 mg/L. The method comprises the following specific steps:
50mg of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt phosphide nanocomposite (CoP-NPS-C) prepared in example 1 is weighed, ultrasonically dispersed in 1L of 50mg/L p-chlorophenol (4-CP) aqueous solution, stirred for 30min, and sampled to be tested. Then, 500mg of PMS was added to the system, and samples were taken at regular intervals to be tested. The sampling operation is as follows: 1mL of sample solution is taken, 1mL of absolute ethyl alcohol is used for quenching, then the sample solution is filtered by a filter membrane of 0.22 mu m, and then 1mL of filtrate is taken to be tested in a liquid phase bottle. Detecting the solution to be detected by High Performance Liquid Chromatography (HPLC), and analyzing the concentration of the parachlorophenol in the solution. In addition, the above materials were not added according to the above method to investigate the ability of PMS alone to oxidatively degrade 4-CP as a control.
The test results show (as shown in FIG. 4) that when only 4-CP and catalyst are present in the reaction system, the 4-CP concentration is only reduced by 0.75% after 30min, and it is possible that the 4-CP is adsorbed on the surface of the material to reduce the concentration, and the adsorption effect is negligible; after PMS is continuously added into the system, the 4-CP degradation rate reaches 90.01 percent in 5min, 98.84 percent in 20min, and the 4-CP is almost completely degraded. Additionally, it can be seen from the figure that when PMS is used alone to oxidatively degrade 4-CP, the concentration of 4-CP is reduced by less than 5% after 20min, indicating that PMS itself has poor oxidative degradation capability to 4-CP. It is thus seen that the degradation of 4-CP is mainly achieved by means of a higher oxidation reaction of PMS activated by a catalyst. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt phosphide nanocomposite prepared by the invention has excellent catalytic activity in the degradation of 4-CP by activating PMS.
Example 5 Performance testing of NPS-codoped porous carbon-loaded manganese phosphide nanocomposite in advanced oxidation of activated peroxymonosulfate
The catalytic performance of the material prepared in example 3 for activating PMS to degrade methylene blue solution was tested with Methylene Blue (MB) as a substrate. The initial concentration of methylene blue in the system is 150mg/L, the initial concentration of the catalyst is 100mg/L, and the initial concentration of PMS is 800 mg/L. The method comprises the following specific steps:
50mg of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded manganese phosphide nanocomposite (MnP-NPS-C) prepared in example 3 is weighed, ultrasonically dispersed in 500mL of 150mg/L Methylene Blue (MB) aqueous solution, stirred for 30min, and sampled to be tested. Then, 400mg of PMS was added to the system, and samples were taken at regular intervals to be tested. The sampling operation is as follows: 2mL of sample solution is taken, quenched by 2mL of absolute ethyl alcohol, filtered by a filter membrane of 0.22 mu m, and then the filtrate is diluted moderately to be tested. And (3) detecting the solution to be detected by an ultraviolet spectrophotometer, and analyzing the concentration change of MB in the solution. In addition, the ability of PMS alone to oxidatively degrade MB was investigated in the same manner as above without adding the above-mentioned materials, to form a control.
From the test results (as shown in fig. 5), when there is only MB and catalyst in the reaction system, the concentration of MB in the solution after 30min is only reduced by 0.14%, which is probably because the surface of the material adsorbs a small amount of MB, and the adsorption is weak and negligible; after PMS is continuously added into the system, MB is degraded to 27.25% in 10min, and the MB degradation rate is 43.03% in 60 min. Moreover, when no catalyst is added in the system, MB in the solution is only degraded by 10.34 percent in 60min, which indicates that the capability of PMS for oxidizing and degrading MB is poor. It follows that the degradation of MB is achieved mainly by means of a higher oxidation reaction of the material catalysing the activated PMS. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded manganese phosphide nanocomposite prepared by the invention has good catalytic activity in the degradation of MB through PMS activation. Example 6 preparation of Nitrogen phosphorus Sulfur codoped porous carbon loaded cobalt-Nickel bimetallic phosphide nanocomposite
The preparation process comprises the following steps:
32.5g (150mmol) of cobalt acetate [ Co (CH) ]3COO)2·4H2O]12.45g (50mol) of nickel acetate [ Ni (CH) ]3COO)2·4H2O]200g of sucrose, 1.2kg of sodium bicarbonate were directly ground to complete mixing; raising the temperature of the mixed powder from room temperature to 500 ℃ at the heating rate of 5 ℃/min in a tubular furnace, pyrolyzing the mixed powder for 8 hours at the temperature of 500 ℃, introducing Ar into the tubular furnace, controlling the flow rate to be about 50mLmin, and reducing the temperature to the room temperature at the heating rate of 5 ℃/min to obtain the CoNi-g-C3N4A material;
200g of CoNi-g-C3N4Carrying out ultrasonic treatment on the material in 16L of benzyl alcohol for 50min to obtain a well-dispersed suspension A; 3L of a benzyl alcohol solution in which 150g of HCCP and 500g of BPS were dissolved was added to suspension A; after mixing for 20min, continuously and slowly dripping 1.6L triethylamine, continuously reacting for 10h, and then carrying out separation operation. In the above process, the suspension was kept in a stirred state at 700 rpm. The reacted material is filtered by an organic mixed nylon new sub-filtration membrane with the aperture of 0.45 mu m, washed by methanol for 2 times and dried in an oven at 60 ℃ for 12 hours to obtain CoNi-g-C3N4@ PZS material;
120g of CoNi-g-C was taken3N4The @ PZS material is pyrolyzed in a tube furnace, the temperature is raised from room temperature to 800 ℃ at the heating rate of 20 ℃/min, the material stays for 7 hours at the temperature of 800 ℃, Ar and PH are introduced into the tube furnace3The flow rate of the mixed gas is controlled to be about 10mL/min, the mixed gas is cooled to 200 ℃ at the speed of 40 ℃/min, and then the mixed gas is naturally cooled to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt-iron bimetal phosphide nano composite material (CoNiP-NPS-C).
Characterization of the materials:
the morphology of the material is characterized by SEM (shown in figure 6) and TEM (shown in figure 7), and the material can be seen to have porous nano flake morphology, the diameter of a flake is about 2-6 μm, and the metal phosphide is highly uniformly dispersed in the nano flake, and the size of the metal phosphide is 5-10 nm.
Example 7 preparation of Nitrogen phosphorus Sulfur codoped porous carbon loaded manganese vanadium bimetallic phosphide nanocomposite
The preparation process comprises the following steps:
49g (200mmol) of manganese acetate [ Mn (CH) ]3COO)2·4H2O]3.7752g (30mmol) of vanadium chloride (VCl)3) 250g of cyanamide and 700g of ammonium chloride are heated and refluxed for 4h at 80 ℃ in deionized water, then the temperature is raised to 120 ℃ until the liquid in the system is evaporated to dryness, the mixture is further dried for 12h in a 120 ℃ oven, and the mixture is ground to obtain completely mixed powder; raising the temperature of the mixed powder from room temperature to 520 ℃ at a heating rate of 40 ℃/min in a tube furnace, pyrolyzing the mixed powder for 12 hours at the temperature of 520 ℃, introducing He into the tube furnace, controlling the flow rate to be about 30mLmin, and naturally cooling to obtain MnV-g-C3N4A material;
260g of MnV-g-C3N4Carrying out ultrasonic treatment on the material in 10L of ethanol for 25min to obtain a well-dispersed suspension A; 1L of an ethanol solution in which 150g of HCCP and 400g of BPS were dissolved was added to suspension A; after mixing for 20min, 150mL of 0.3M sodium hydroxide solution was continuously and slowly added dropwise, and the reaction was continued for 32h, followed by separation. In the above process, the suspension was kept in a stirred state at 950 rpm. The reacted material is filtered by an organic mixed nylon new sub-filtration membrane with the aperture of 0.45 mu m, washed by ethanol for 4 times and dried in an oven at 80 ℃ for 16 hours to obtain MnV-g-C3N4@ PZS material;
taking 300g of MnV-g-C3N4The @ PZS material is pyrolyzed in a tube furnace, the temperature is raised from room temperature to 860 ℃ at the temperature rise rate of 15 ℃/min, the material stays for 15H at 860 ℃, He and H are introduced into the tube furnace2And (3) controlling the flow rate of the mixed gas of S to be about 35mL/min, reducing the temperature to 100 ℃ at the speed of 15 ℃/min, naturally cooling, and cooling to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded manganese-vanadium bimetallic phosphide nano composite material (MnVP-NPS-C).
Characterization of the materials:
the morphology of the material is characterized by SEM (shown in figure 8), and the material is shown to be in the shape of a nano-flake, the surface of the material is loose and porous, and the diameter of the flake is about 1-2 μm.
Example 8 Performance test of nitrogen phosphorus and sulfur co-doped porous carbon loaded cobalt nickel phosphide nanocomposite in activated persulfate advanced oxidation
And (3) testing the catalytic performance of the material for activating PS to degrade the RhB solution by using rhodamine B (RhB) as a substrate. In the system, the initial concentration of RhB is 200mg/L, the initial concentration of the catalyst is 80mg/L, and the initial concentration of PS is 600 mg/L.
The method comprises the following specific steps:
160mg of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt-nickel phosphide nanocomposite prepared in example 6 was ultrasonically dispersed in 2L of 200mg/L RhB solution, stirred for 30min, and sampled to be tested. Then, 900mgPS was added to the system and samples were taken at intervals to be tested. The sampling operation is as follows: 2mL of sample solution is taken, quenched by 2mL of absolute ethyl alcohol, filtered by a filter membrane of 0.22 mu m, and then the filtrate is diluted moderately to be tested. And detecting the solution to be detected by an ultraviolet spectrophotometer, and analyzing the concentration change of RhB in the solution. In addition, the ability of PS alone to oxidatively degrade RhB was investigated as a control without adding a catalyst according to the above method.
The test results showed (as shown in fig. 9) that when there was only RhB and catalyst in the reaction system, RhB decreased by 2.05% after 30min, and that stage was adsorption of RhB on the catalyst surface and the amount of adsorption was small. After PS is continuously added into the system, the degradation rate of RhB reaches 68.85% in 2min, 83.21% in 5min, 93.79% in 20min, 97.33% in 60min and RhB is almost completely degraded. And when the RhB is degraded by oxidizing with the PS alone, the concentration of the 4-CP is only reduced by 8.5% after 60min, which shows that the good removal effect cannot be achieved by oxidizing and degrading the RhB with the PS alone. It follows that RhB degradation is achieved by virtue of the material activating PS to generate reactive free radicals. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded cobalt-nickel bimetallic nanocomposite prepared by the invention has excellent catalytic activity in the degradation of RhB by activating PS.
Example 9 performance testing of nitrogen phosphorus sulfur co-doped porous carbon loaded manganese vanadium phosphide nanocomposite in activated peroxymonosulfate advanced oxidation
And (3) testing the catalytic performance of the material for activating PMS to degrade TC solution by using Tetracycline (TC) as a substrate. In the system, the initial concentration of tetracycline is 120mg/L, the initial concentration of the catalyst is 200mg/L, and the initial concentration of PMS is 1 g/L.
The method comprises the following specific steps:
800mg of the nitrogen-phosphorus-sulfur co-doped porous carbon loaded manganese vanadium phosphide nanocomposite prepared in example 7 is ultrasonically dispersed in 4L of 120mg/L TC solution, stirred for 30min, and sampled to be tested. Then, 3.2g of PMS was added to the system, and samples were taken at regular intervals to be tested. The sampling operation is as follows: 2mL of sample solution is taken, quenched by 2mL of anhydrous methanol, filtered by a filter membrane of 0.22 mu m, and then the filtrate is diluted moderately and is to be tested. And detecting the solution to be detected by an ultraviolet spectrophotometer, and analyzing the concentration change of TC in the solution.
The test results showed (as shown in fig. 10) that when only TC and catalyst were present in the reaction system, the TC was reduced by 3.87% after 30min, and the adsorption of TC on the surface of the material occurred at this stage with a smaller amount of adsorption. When PMS is continuously added into the system, the TC is degraded by 56.28% in 10min, the degradation rate reaches 79.19% in 40min, and most of the TC is degraded. When the materials are not added in the system, the oxidation of PMS is solely relied on, the removal rate of TC is only 6% at 60min, and the degradation effect is poor. Thus, the degradation of TC is mainly achieved by means of material activation PMS. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded manganese-vanadium bimetallic nanocomposite prepared by the invention has good catalytic activity in the degradation of tetracycline by activating PMS.
Example 10 preparation of Nitrogen phosphorus Sulfur codoped porous carbon loaded platinum iron copper trimetal phosphide nanocomposite
The preparation process comprises the following steps:
2.8992g (12mmol) of copper nitrate [ Cu (NO)3)2·3H2O]2.7030g (10mmol) of iron chloride (FeCl)3·6H2O), 1.0358g (2mmol) of chloroplatinic acid (H)2PtCl6·6H2O), 28g of citric acid and 135g of ammonium chloride are heated and refluxed for 10 hours at 70 ℃ in deionized water, then the temperature is raised to 110 ℃ until the liquid in the system is evaporated to dryness, and the mixture is dried in 110 DEGFurther drying in a baking oven at the temperature of 36 hours, and grinding to obtain completely mixed powder; raising the temperature of the mixed powder from room temperature to 530 ℃ at the heating rate of 40 ℃/min in a tubular furnace, pyrolyzing the mixed powder for 8 hours at the temperature of 530 ℃, introducing mixed gas of He and Ar into the tubular furnace, controlling the flow rate to be 35-40mL/min, and carrying out programmed cooling at the speed of 15 ℃/min to obtain PtFeCu-g-C3N4A material;
15g of PtFeCu-g-C3N4Carrying out ultrasonic treatment on the material in 1L of acetonitrile for 30min to obtain a well-dispersed suspension A; 500mL of acetonitrile solution in which 40g of HCCP and 100g of BPS were dissolved was added to suspension A; after mixing for 40min, a mixture of 150mL of diethylamine and 100mL of acetonitrile was added dropwise continuously and slowly, and the reaction was continued for 15 hours, followed by separation. The reacted material is filtered by an organic mixed nylon new sub-filtration membrane with the aperture of 0.45 mu m, washed for 2 times by acetonitrile and dried for 7 hours in a drying oven at the temperature of 90 ℃ to obtain PtFeCu-g-C3N4@ PZS material;
20g of PtFeCu-g-C was taken3N4The @ PZS material is pyrolyzed in a tubular furnace, the temperature is increased from room temperature to 1150 ℃ at the temperature rising rate of 45 ℃/min, the material stays for 8 hours at the temperature of 1150 ℃, He and NH are introduced into the tubular furnace3And pH3The flow rate of the mixed gas is controlled to be 10-20mL/min, and the nitrogen, phosphorus and sulfur co-doped porous carbon loaded platinum-titanium-iron trimetal phosphide nano composite material (PtFeCu-NPS-C) is obtained after natural cooling.
Characterization of the materials:
the morphology of the material is characterized by TEM (as shown in FIG. 11), and it can be seen that the material is in the form of nano-flakes, which are loose, and the metal phosphide is uniformly dispersed on the nano-flakes, and the size of the metal phosphide is about 5-15 nm.
Example 11 preparation of nitrogen phosphorus sulfur co-doped porous carbon loaded nickel phosphide nanocomposite and Performance testing thereof in advanced Oxidation of activated peroxymonosulfate
The preparation process comprises the following steps:
249g (1mol) of nickel acetate [ Ni (CH) ]3COO)2·4H2O]Heating and refluxing 2kg of starch and 6kg of ammonium chloride in 4L of deionized water at 80 ℃ for 4 hours to obtain a completely dissolved mixed solution, and then risingEvaporating deionized water to dryness at high temperature of 150 ℃, and completely drying in a drying oven at 150 ℃ to obtain powder with the three uniformly mixed; raising the temperature of the mixed powder from room temperature to 550 ℃ in a tubular furnace, pyrolyzing the mixed powder for 15h at the temperature of 550 ℃, wherein the heating rate is 10 ℃/min, introducing Ar into the tubular furnace, controlling the flow rate to be 20-30mL/min, reducing the temperature to 200 ℃ at the rate of 20 ℃/min, and naturally cooling to obtain Ni-g-C3N4A material;
500g of Ni-g-C3N4Carrying out ultrasonic treatment on the material in 30L of propanol for 25min to obtain a well-dispersed suspension A; 4L of a propanol solution in which 1kg of HCCP and 2.4kg of BPS were dissolved was added to suspension A; after mixing for 20min, continuously and slowly dripping 1L of 0.5M ammonia water, continuously reacting for 48h, and then carrying out separation operation. Standing the reacted system to allow the material to naturally settle, removing the supernatant, vacuum-filtering with an organic mixed nylon new sub-filtration membrane with pore diameter of 0.45 μm to remove the residual liquid component, washing with methanol for 8 times, and drying in an oven at 100 deg.C for 24h to obtain Ni-g-C3N4@ PZS material;
1kg of Ni-g-C was taken3N4The @ PZS material is pyrolyzed in a tubular furnace, the temperature is raised from room temperature to 1200 ℃ at the heating rate of 6 ℃/min, the material stays for 18h at 1200 ℃, Ar and N are introduced into the tubular furnace2、He、H2S and PH3The flow rate of the mixed gas is controlled to be 10-15mL/min, and the temperature is reduced at the speed of 20 ℃/min to obtain the nitrogen-phosphorus-sulfur co-doped porous carbon loaded nickel phosphide nano composite material (NiP-NPS-C).
Characterization of the materials:
the crystal phase of the product is identified as nickel phosphide by an X-ray powder diffractometer (as shown in figure 12);
testing the catalytic performance of the material:
acyclovir (ACV) is used as a substrate, and the catalytic performance of the material for activating PMS to degrade ACV solution is tested. In the system, the initial concentration of ACV is 25mg/L, the initial concentration of the catalyst is 60mg/L, and the initial concentration of PMS is 800 mg/L. The method comprises the following specific steps:
and (3) ultrasonically dispersing 600mg of the prepared nitrogen-phosphorus-sulfur co-doped porous carbon loaded nickel phosphide nanocomposite in 10L of 25mg/L ACV solution, stirring for 30min, and sampling to be tested. Then, 8g of PMS was added to the system, and samples were taken at regular intervals to be tested. The sampling operation is as follows: 1mL of sample solution is taken, 1mL of absolute ethyl alcohol is used for quenching, then the sample solution is filtered by a filter membrane of 0.22 mu m, and then 1mL of filtrate is taken to be tested in a liquid phase bottle. And detecting the solution to be detected by High Performance Liquid Chromatography (HPLC), and analyzing the concentration of the ACV in the solution.
The test results show (as shown in fig. 13) that when only ACV and catalyst are present in the reaction system, the concentration of ACV decreases by 0.61% at 30min, indicating that the material itself has a smaller amount of ACV adsorption. When PMS is continuously added into the system, ACV is degraded by 40.27% in 5min, and the total degradation rate is 68.57% in 40 min. Additionally, it can be seen from the figure that when PMS alone oxidatively degrades ACV, only 5.67% of ACV is removed after 60min, indicating that PMS itself has a weak oxidative degradation capability to AVC. It is thus seen that the material is able to activate PMS to play a major role in degrading ACV. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded nickel phosphide nanocomposite prepared by the invention has good catalytic activity in activating PMS to degrade ACV.
Example 12 preparation of nitrogen phosphorus and sulfur co-doped porous carbon loaded iron molybdenum bimetallic phosphide nanocomposite and performance test thereof in advanced oxidation of activated hydrogen peroxide
The preparation process comprises the following steps:
30g (150mmol) of ferric nitrate [ Fe (NO) ]3)3·9H2O]16g (80mmol) of molybdenum trichloride (MoCl)3) 100g glucose, 200g ammonium bicarbonate were directly ground to obtain a completely mixed powder; raising the temperature of the mixed powder from room temperature to 550 ℃ at the heating rate of 8 ℃/min in a tubular furnace, carrying out pyrolysis at 550 ℃ for 3h, and introducing N into the tubular furnace2The flow rate is controlled to be 20-25mL/min, and FeMo-g-C is obtained after natural cooling3N4A material;
40g of FeMo-g-C3N4Carrying out ultrasonic treatment on the material in 15L of ethanol for 25min to obtain a well-dispersed suspension A; 900mL of an ethanol solution in which 200g of HCCP and 200g of BPS were dissolved was added to suspension A; after mixing for 20min, continuously and slowly dripping a mixed solution of 400mL of triethylamine and 200mL of ethanol, continuously reacting for 10h, and then carrying out separation operation. The system after the reaction is firstly communicatedStanding to naturally settle the material, removing supernatant, centrifuging with ethanol for 6 times, and drying in 75 deg.C oven for 14 hr to obtain FeMo-g-C3N4@ PZS material;
80g of FeMo-g-C is taken3N4The @ PZS material is pyrolyzed in a tubular furnace, the temperature is increased to 920 ℃ from room temperature at the heating rate of 6 ℃/min, the material stays for 2 hours at 920 ℃, Ar and N are introduced into the tubular furnace2The flow rate of the mixed gas is controlled to be 20-25mL/min, and the nitrogen, phosphorus and sulfur co-doped porous carbon loaded iron-molybdenum bimetal phosphide nano composite material (FeMoP-NPS-C) is obtained after natural cooling.
Characterization of the materials:
by characterizing the morphology of the material by SEM (shown in FIG. 14) and TEM (shown in FIG. 15), it can be seen that the material is in the form of nanosheets, the diameter of the nanosheets is about 3-4 μm, the metal phosphide is highly uniformly dispersed on the nanosheets, and the size of the metal phosphide is about 2-10 nm.
Testing the catalytic performance of the material:
test materials activated H with bisphenol A (BPA) as substrate2O2Degrading the catalytic performance of the BPA solution. The initial concentration of BPA in the system is 80mg/L, the initial concentration of the catalyst is 100mg/L, H2O2The initial concentration was 1.5 g/L.
The method comprises the following specific steps:
and (3) ultrasonically dispersing 2g of the prepared nitrogen-phosphorus-sulfur co-doped porous carbon loaded iron-molybdenum bimetal phosphide nanocomposite in 20L of BPA solution of 80mg/L, stirring for 30min, and sampling to be tested. Then, 30g H was added to the system2O2Samples are taken at intervals for testing. The sampling operation is as follows: 1mL of sample solution is taken, 1mL of absolute ethyl alcohol is used for quenching, then the sample solution is filtered by a filter membrane of 0.22 mu m, and then 1mL of filtrate is taken to be tested in a liquid phase bottle. And detecting the solution to be detected by High Performance Liquid Chromatography (HPLC), and analyzing the concentration of BPA in the solution.
The test results showed (as shown in FIG. 16) that when only BPA and catalyst were present in the reaction system, the concentration of BPA decreased by 1.85% after 30min and the BPA adsorbed on the catalyst surface in small amounts. The above system is added with H2O2Then, 5min, 20min, 40minThe degradation rates of BPA were 44.84%, 71.37% and 81.78%, respectively, with BPA being mostly degraded at 40 min. When only H is contained in the system2O2When BPA is subjected to oxidative degradation, 93.77 percent of BPA is still not removed after 40min of reaction, which shows that H2O2The ability to oxidatively degrade BPA is insufficient. Thus, the catalyst plays a major role, being able to activate H2O2And the degradation of BPA is realized. The nitrogen-phosphorus-sulfur co-doped porous carbon loaded iron-molybdenum bimetal phosphide nano composite material prepared by the invention is used for activating H2O2Has good catalytic activity in degrading BPA.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
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 MPx-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).
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