CN111250128A - Composite photocatalyst CNB-CdLa2S4, and preparation and application thereof - Google Patents
Composite photocatalyst CNB-CdLa2S4, and preparation and application thereof Download PDFInfo
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- CN111250128A CN111250128A CN201811467989.1A CN201811467989A CN111250128A CN 111250128 A CN111250128 A CN 111250128A CN 201811467989 A CN201811467989 A CN 201811467989A CN 111250128 A CN111250128 A CN 111250128A
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 10
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- POYSFWLVSUPUCS-UHFFFAOYSA-N [O-][N+](=O)SNC#N Chemical compound [O-][N+](=O)SNC#N POYSFWLVSUPUCS-UHFFFAOYSA-N 0.000 claims description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 abstract description 24
- 229950011260 betanaphthol Drugs 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 22
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- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical compound O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention provides a composite photocatalyst CNB-CdLa2S4Preparation and application thereof, namely CNB and CdLa are prepared by a hydrothermal method2S4Composite photocatalyst CNB-CdLa with different mass ratios2S4And 2-naphthol (a main phenolic pollutant in water) is taken as a model compound of the photocatalytic reaction to evaluate CNB-CdLa2S4The visible light catalytic activity of the composite photocatalyst; under the irradiation of visible light, the degradation rate of the composite photocatalyst on 2-naphthol can reach 85.2 percent; the preparation method provided by the invention is simple to operate and is beneficial to industrial popularization and application.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a composite photocatalyst CNB-CdLa for treating phenol wastewater and chemical wastewater2S4And preparation and application thereof.
Background
With the rapid development of modern industry, the current problem of water pollution has become a great problem facing and urgently awaiting solution for human beings in this century. Among them, phenols in water are the most harmful pollutant, and have strong toxicity and carcinogenicity. In recent years, techniques such as activated carbon adsorption, biodegradation, heat treatment and the like have been developed to remove phenolic pollutants.
g-C3N4The photocatalytic material is a novel photocatalytic material due to the outstanding advantages of high photocatalytic activity, good stability, low price of raw materials and no metal, however, the single-phase catalyst usually has unsatisfactory photocatalytic performance due to low quantum efficiency. Due to g-C3N4The material has high photoproduction electron-hole recombination rate, so that the catalytic efficiency is low, and the application of the material in photocatalysis is limited.
To increase g-C3N4In recent years, many modification methods have been studied. For g-C3N4The nonmetallic elements to be modified include S, N, C, B, F, P, etc., which are believed to substitute C, N, H elements in the 3-s-triazine structural unit to form g-C3N4The lattice defect enables the photoproduction electron-hole pair to be effectively separated, and the photocatalysis performance of the photoproduction electron-hole pair is effectively improved.
Zhang et al mix dicyandiamide with BmimPF6 (ionic liquid), and calcine at high temperature to obtain P-doped g-C3N4XPS analysis shows that P element replaces C in a structural unit, and a small amount of P doping can not change g-C3N4However, it significantly changes g-C3N4The photo-generated current of the electronic structure is obviously higher than that of undoped g-C3N4. Yan et al prepared B-doped g-C by thermal decomposition of a mixture of melamine and boron oxide3N4XPS spectral analysis shows that B replaces g-C3N4Research on H in the structure and photocatalytic degradation dye shows that the doping of B improves the absorption of the catalyst to light, and the photocatalytic degradation efficiency of rhodamine B is improved.
Liu et al will react g-C3N4At H2Calcining at 450 ℃ in S atmosphere to prepare the S element doped g-C with unique electronic structure3N4XPS analysis shows that S replaces g-C3N4In the structure N. S-doped g-C when lambda > 300 and 420nm3N4The catalytic efficiency of the photocatalytic decomposition of hydrogen produced by water is respectively higher than that of single g-C3N4The improvement is 7.2 and 8.0 times. Wang et al reported that B, F was doped with g-C3N4Study, they used NH4F is used as an F source to prepare F element doped g-C with DCDA3N4Catalyst (CNF). The research result shows that the F element is doped into g-C3N4In the skeleton of (2), a C-F bond is formed so that a part of sp is present2Conversion of C to sp3C, thereby resulting in g-C3N4The plane structure is irregular. In addition, as the doping amount of the F element is increased, the absorption range of the CNF in a visible light region is enlarged, and the corresponding band gap energy is reduced from 2.69eV to 2.63 eV.
However, these techniques still have the defects of low treatment efficiency, easy generation of secondary pollutants, long reaction time and the like.
Therefore, it is important to develop a low-cost, fast and environment-friendly composite photocatalyst for efficiently removing phenolic pollutants in water.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: composite photocatalyst CNB-CdLa2S4Preparation and application thereof, namely CNB and CdLa are prepared by a hydrothermal method2S4Novel CNB-CdLa with different mass ratios2S4A composite photocatalyst and 2-naphthol (a main phenol pollutant in water) as the photocatalystA model compound of chemical reaction was evaluated for CNB-CdLa2S4The visible light catalytic activity of the composite photocatalyst, and thus the present invention has been completed.
The object of the present invention is to provide the following:
in a first aspect, the present invention provides a composite photocatalyst comprising boron-doped graphite-phase carbon nitride and a metal sulfide.
Wherein the metal sulfide is a single metal sulfide or a multi-metal sulfide, and is preferably a multi-metal sulfide.
Wherein, the metal elements in the multi-metal sulfide are two of cadmium, lanthanum, terbium, europium, cerium, samarium and dysprosium, and cadmium and lanthanum are more preferable.
Wherein the composite photocatalyst is CNB-CdLa2S4Preferably, in the XRD pattern thereof, diffraction peaks appear at 13.4 °, 17.66 °, 23 °, 24.35 °, 26.48 °, 28.02 °, 30.45 °, 35.86 °, 42.94 °, 43.94 °, 46.78 °, 50.02 °, 53.46 °, 57.18 °, 60.88 °, 63.14 °, 68.06 °, 70.92 °, more preferably CdLa2S4Dispersed on the surface of the CNB sheet layer as nano-particles.
In a second aspect, the present invention also provides a method for preparing a composite photocatalyst, preferably for preparing a composite photocatalyst as described in the first aspect, the method comprising the steps of:
and 2, preparing the composite photocatalyst.
In a third aspect, the use of the composite photocatalyst according to the first aspect or the composite photocatalyst prepared by the method according to the second aspect, for degrading contaminated wastewater, preferably for degrading wastewater containing phenols.
Drawings
Figure 1 shows the X-ray diffraction pattern of comparative example 1 and a CNB catalyst sample;
FIG. 2 shows comparative example 2, products of examples 1 to 4 and CNB5XRD pattern of (a);
FIG. 3 shows comparative example 2, products of examples 1 to 4 and CNB5XRD pattern of (a);
FIG. 4 shows photoluminescence spectra of comparative example 1 and a CNB series of samples;
fig. 5 shows fourier transform infrared spectra of comparative example 1 and CNB series samples;
FIG. 6 shows comparative example 2, products of examples 1 to 4 and CNB5An infrared spectrum of (1);
FIG. 7 shows comparative example 2, products of examples 1 to 4 and CNB5TEM and HR-TEM images of;
fig. 8 shows a graph of catalytic activity for comparative example 1 and CNB series samples;
FIG. 9 shows comparative example 2, products of examples 1 to 4 and CNB5Catalytic activity diagram (c).
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
The inventor finally researches and treats CNB-CdLa of phenolic sewage through a large number of research experiments2S4A composite photocatalyst is provided. To date, no report on the composite photocatalyst has been found.
According to a first aspect of the present invention, there is provided a composite photocatalyst comprising boron doped graphite phase carbon nitride (g-C)3N4B) And metal sulfides.
Wherein the metal sulfide is a single metal sulfide or a multi-metal sulfide, and is preferably a multi-metal sulfide.
In one embodiment, the metal elements in the multimetallic sulfide are two of cadmium, lanthanum, terbium, europium, cerium, samarium, dysprosium.
In a preferred embodiment, the metal elements in the multimetallic sulfide are cadmium (Cd) and lanthanum (La).
Further preferably, in the multimetal sulfide, the molar ratio of the cadmium element to the lanthanum element is 1: 2.
Further preferably, the mass ratio of the boron-doped graphite-phase carbon nitride to the polymetallic sulfide is (10-95): 100, such as 25:100, 50:100, 75:100, 80: 100.
The composite photocatalyst is CNB-CdLa2S4Preferably, in the XRD pattern thereof, diffraction peaks appear at 13.4 °, 17.66 °, 23 °, 24.35 °, 26.48 °, 28.02 °, 30.45 °, 35.86 °, 42.94 °, 43.94 °, 46.78 °, 50.02 °, 53.46 °, 57.18 °, 60.88 °, 63.14 °, 68.06 °, 70.92 °, more preferably CdLa2S4Dispersed on the surface of the CNB sheet layer as nano-particles.
The inventor surprisingly discovers that the composite photocatalyst CNB-CdLa provided by the invention2S4Can effectively degrade the phenol wastewater by photocatalysis, and the degradation rate of the 2-naphthol can reach 85.2 percent.
According to a second aspect of the present invention, there is provided a method for preparing a composite photocatalyst, comprising the steps of:
and 2, preparing the composite photocatalyst.
Wherein, step 1 includes the following steps:
step 1-1, dissolving a carbon nitrogen source and a boron source in a solvent, and uniformly mixing;
step 1-2, removing the solvent;
and 1-3, roasting, and performing post-treatment to obtain the boron-doped graphite-phase carbon nitride CNB.
Wherein the content of the first and second substances,
step 1-1In (1),
the carbon-nitrogen source is selected from melamine, cyanamide and urea; preferably urea;
the boron source is selected from boron oxide, boric acid and sodium tetraphenylborate; preferably sodium tetraphenylborate;
the solvent is selected from distilled water, deionized water and purified water; preferably distilled water.
In one embodiment, the dosage ratio of the carbon nitrogen source to the boron source is 10g (0-0.1) g;
in a preferred embodiment, the ratio of the amount of carbon nitrogen source to the amount of boron source is 10g: (0.001-0.5) g, such as 10g:0.005g, 10g: 0.01g, 10g: 0.015 g.
In a preferred embodiment, the solvent is distilled water. The amount of the solvent is that the ratio of the mass of the carbon-nitrogen source to the volume of the solvent is 10g: (10-40) mL, such as 10g: 20 mL.
Step 1-2The temperature for removing the solvent is 70-90 ℃;
the present inventors have found that the removal of the solvent from the system containing the mixture of the carbon nitrogen source and the boron source can significantly shorten the calcination time, and therefore, the present invention selects the removal of the solvent before calcination, and the present invention is not particularly limited to the manner of removing the solvent, and any manner of removing the solvent in the prior art can be used, such as normal temperature volatilization, normal pressure heating, reduced pressure distillation, etc., and the present invention is not particularly limited to the temperature at which the solvent is removed, so as not to decompose the carbon nitrogen source and the boron source, preferably 70 to 90 ℃, such as 80 ℃.
The inventor also finds that the mixture after the solvent is removed is easier to react under the condition of high-temperature calcination, the reaction time can be obviously shortened, and the obtained product has good appearance and uniform particle size.
The inventors have found that a carbon-nitrogen source and a boron source can form boron-doped graphite-phase carbon nitride, i.e., g-C, with good properties when calcined at 450 ℃ to 650 ℃, more preferably 550 ℃3N4B (CNB), and the prepared product has uniform appearance.
In a preferred embodiment, the calcination is carried out for a period of 1 to 4 hours, such as 2 hours.
In the invention, the infrared spectrogram of the prepared CNB is 810cm-1、1240cm-1、1320cm-1、1400cm-1、1430cm-1、1570cm-1、1640cm-1And 3100--1There is an absorption peak.
In step 2, step 2 comprises the following steps:
step 2-1, dissolving the raw materials in a dispersing agent and uniformly mixing;
step 2-2, carrying out heat preservation reaction;
and 2-3, drying to obtain a final product.
Wherein the content of the first and second substances,
in the step 2-1, the raw materials comprise metal nitrate, a sulfur source and boron-doped graphite-phase carbon nitride;
the dispersant is water, preferably distilled water, purified water and deionized water; more preferably distilled water.
Preferably, the first and second electrodes are formed of a metal,
in the step 2-1, the metal nitrate is selected from two of cadmium nitrate, lanthanum nitrate, terbium nitrate, europium nitrate, cerium nitrate, samarium nitrate and dysprosium nitrate; more preferably cadmium nitrate or lanthanum nitrate.
In the invention, the cadmium nitrate is cadmium nitrate of four crystal waters; the lanthanum nitrate used is lanthanum nitrate with six crystal waters. The molar ratio of the cadmium nitrate tetrahydrate to the lanthanum nitrate hexahydrate is 1: 2.
The sulfur source is selected from thiourea, ammonium thiocyanate and nitrothiocyanamide; more preferably thiourea.
Further preferably, the molar ratio of the cadmium nitrate to the thiourea is 1: 4.
In a preferred embodiment, the cadmium nitrate tetrahydrate, the lanthanum nitrate hexahydrate, the thiourea, the deionized water and the boron-doped graphite-phase carbon nitride are mixed and stirred for 1-4 hours, such as 2 hours; then carrying out the heat preservation reaction of the step 2-2.
The inventor finds that the step 2-1 needs to be stirred for a certain time, preferably 2 hours, so that the raw materials are mixed more uniformly, and the photocatalytic activity of the final product is best.
In the step 2-2, the temperature of the heat preservation reaction is 140-180 ℃, such as 160 ℃; the reaction time is kept for 12-96 h, such as 72 h.
In the step 2-3, the drying temperature is 50-70 ℃; preferably, the step 2-3 further comprises cooling the system obtained in the step 2-2 to room temperature before drying, and then centrifuging. The centrifugal separation is to remove the water solution; and cleaning the solid obtained after centrifugal separation by using a solvent II to clean impurities on the surface of the solid.
The solvent II comprises absolute ethyl alcohol and distilled water, and is washed by the absolute ethyl alcohol and then by the distilled water.
In a further preferred embodiment, the drying temperature is 60 ℃ and the drying time is 24 h.
The inventor finds that the drying temperature is 60 ℃, the drying time is 24 hours, and the obtained composite photocatalyst CNB-CdLa2S4The performance is better.
The composite photocatalyst CNB-CdLa prepared by the method provided by the invention2S4In the XRD diagram, diffraction peaks appear at 13.4 °, 17.66 °, 23 °, 24.35 °, 26.48 °, 28.02 °, 30.45 °, 35.86 °, 42.94 °, 43.94 °, 46.78 °, 50.02 °, 53.46 °, 57.18 °, 60.88 °, 63.14 °, 68.06 ° and 70.92 °. CNB-CdLa2S4The composite photocatalyst has both a diffraction peak of CNB and CdLa2S4The diffraction peak of (A) indicates CNB-CdLa2S4CNB and CdLa in composite photocatalyst2S4Two phases coexist.
In the TEM image, 80% CNB-CdLa2S4Cdla in the composite catalyst of (2)2S4The nanoparticles are dispersed on the surface of the CNB sheet.
According to a third aspect of the present invention, there is provided a use of the composite photocatalyst described in the first aspect above or the composite photocatalyst prepared by the preparation method described in the second aspect, for degrading contaminated wastewater, preferably for degrading wastewater containing phenols.
In the invention, 2-naphthol (a main phenol pollutant in water) is used as a model compound for photocatalytic reaction; the composite photocatalyst provided by the invention has the degradation rate of 85.2% for 2-naphthol under the irradiation of visible light for 4 hours.
The inventor believes that this may be because after recombination of two semiconductors with matched band structures, the photogenerated carriers can be transferred and separated between different energy levels, so that the lifetime of the carriers is prolonged, and the photocatalytic reaction activity is improved.
And from the UV-visible spectrumTo show that CNB is carbon nitride with boron-doped graphite phase5In contrast, CNB-CdLa2S4The absorption intensity of the composite photocatalyst in a 400-plus-800 nm visible light region is obviously enhanced, and the absorption wave also moves towards the long wave direction, which shows that the boron-doped graphite-phase carbon nitride CNB and CdLa2S4Synergistic effect may occur, so as to increase the light absorption range and light absorption intensity and make CNB-CdLa2S4The composite photocatalyst can more effectively utilize visible light, thereby being beneficial to enhancing the photocatalytic activity.
The composite photocatalyst CNB-CdLa provided by the invention2S4And the preparation and the application thereof have the following beneficial effects:
(1) the composite photocatalyst provided by the invention can be used for treating polluted wastewater, and is preferably used for photodegrading phenol wastewater;
(2) the composite photocatalyst provided by the invention has high photocatalytic activity, and the photocatalytic degradation rate of 2-naphthol can reach 85.2% under the irradiation of visible light for 4 hours;
(3) the composite photocatalyst provided by the invention has the advantages of low cost, wide raw material source and environmental protection;
(4) the preparation method of the composite photocatalyst provided by the invention is simple to operate and is beneficial to industrial popularization.
Examples
3 4Preparation of boron-doped graphite-phase carbon nitride (g-CNB)：
Mixing 10g of urea with 0.005g of sodium tetraphenylborate in 20mL of distilled water, 0.010g of sodium tetraphenylborate in 0.015g of sodium tetraphenylborate in 0.010g of distilled water, and stirring;
then evaporating the water to dryness in a water bath at 80 ℃;
then putting the solid after evaporation into a crucible, calcining for 2h at 550 ℃ in a muffle furnace, cooling to room temperature, grinding to respectively obtain boron-doped graphite-phase carbon nitride (g-C)3N4B) Samples, individually labeled CNB5、CNB10、CNB15。
Example 1
Take 0.5949gCd (NO)3)2·4H2O、1.6700g La(NO3)3·6H2O and 1.4200g of thiourea were added to a beaker containing 70mL of deionized water, and 0.2500g of boron-doped graphite-phase carbon nitride CNB was added5Continuously stirring for 2h until a milk-shaped suspension is formed;
then placing the suspension in a reaction kettle to react for 72 hours at 160 ℃;
cooling to room temperature, performing centrifugal separation, washing the solid product with a small amount of anhydrous ethanol and distilled water respectively, drying at the constant temperature of 60 ℃ for 24 hours, and grinding at room temperature to obtain the composite photocatalyst which is marked as 25% CNB-Cdla2S4。
Example 2
This example is the same as example 1 except that boron-doped graphite-phase carbon nitride CNB was used5Of boron-doped graphite-phase carbon nitride CNB used in this example50.5000 g; the obtained composite photocatalyst product is marked as 50 percent CNB-CdLa2S4。
Example 3
This example is the same as example 1 except that boron-doped graphite-phase carbon nitride CNB was used5Of boron-doped graphite-phase carbon nitride CNB used in this example50.7500 g; the obtained composite photocatalyst product is marked as 75% CNB-CdLa2S4。
Example 4
This example is the same as example 1 except that boron-doped graphite-phase carbon nitride CNB was used5Of boron-doped graphite-phase carbon nitride CNB used in this example50.8000 g; the obtained composite photocatalyst product is marked as 80% CNB-CdLa2S4。
Comparative example
3 4Comparative example 1 preparation of g-CN
Taking 10g of urea and uniformly stirring in 20mL of distilled water;
then evaporating the water to dryness in a water bath at 80 ℃;
then evaporating to drynessPlacing the solid into a crucible, calcining at 550 ℃ for 2h in a muffle furnace, cooling to room temperature, and grinding to obtain graphite phase carbon nitride (g-C)3N4) Sample, labeled CN.
2 4Comparative example 2 preparation of CdLaS
Take 0.5949gCd (NO)3)2·4H2O、1.6700g La(NO3)3·6H2O and 1.4200g of thiourea were added to a beaker containing 70mL of deionized water and stirring was continued for 2 h;
then placing the system in a reaction kettle to react for 72 hours at 160 ℃;
cooling to room temperature, centrifuging, washing the solid product with small amount of anhydrous ethanol and distilled water, drying at 60 deg.C for 24 hr, and grinding at room temperature to obtain polymetallic sulfide (named as CdA)2S4。
Examples of the experiments
XRD analysis of sample of Experimental example 1
The CNB-series catalysts of comparative examples 1-2 and CNB series and the CNB-CdLa of examples 1-4 were measured2S4XRD spectrograms of series catalyst samples are respectively pressed into thin slices (only central covering is needed), after pressing, scanning spectrograms are carried out by an XD-3 diffractometer, in order to save time and obtain good scanning results, the parameters of the scanning speed are set to be 8deg/min, the scanning range is 10-80 deg., and the results are shown in figure 1 and figure 2.
FIG. 1 shows CN, CNB5，CNB10，CNB15XRD pattern of (a);
in FIG. 2, (a) CdLa2S4；(b)25％CNB-CdLa2S4；(c)50％CNB-CdLa2S4；(d)75％CNB-CdLa2S4；(e)80％CNB-CdLa2S4；(f)CNB5；
As can be seen from fig. 1, two characteristic diffraction peaks were present for all samples. Of these two diffraction peaks, 13.4 ° 2 θ corresponds to a characteristic peak of the CN (100) crystal plane, and 27.3 ° 2 θ corresponds to a characteristic peak of the CN (002) crystal plane. It can also be seen from fig. 1 that: with the increase of the amount of the sodium tetraphenylborate, the characteristic peaks generated by the (100) and (002) crystal planes of the CN are not subjected to angle shift phenomenon and no new peak is generated, which indicates that the CN crystal lattice is not changed after the CN is doped with boron.
As can be seen from fig. 2, for the CNB catalyst sample, the diffraction peaks at diffraction angles 2 θ of 13.4 ° and 23 ° correspond to the (100) and (002) crystal plane diffraction, respectively. For CdLa2S4The diffraction peaks of the catalyst sample when the diffraction angle 2 θ is 17.66 °, 24.35 °, 26.48 °, 28.02 °, 30.45 °, 35.86 °, 42.94 °, 43.94 °, 46.78 °, 50.02 °, 53.46 °, 57.18 °, 60.88 °, 63.14 °, 68.06 °, and 70.92 ° correspond to the crystal planes (100), (120), (121), (220), (300), (222), (401), (303), (420), (421), (422), (501), (521), (522), (531), (602), and (533), respectively, and all the diffraction peak positions are the same as the CdLa crystal plane2S4The standard cards of (1) conform to;
all CNB-CdLa2S4In the composite photocatalyst sample, the diffraction angle 2 theta of 26.48 degrees corresponds to CdLa2S4Crystal plane (220). CNB-CdLa2S4The composite photocatalyst has both a diffraction peak of CNB and CdLa2S4The diffraction peak of (A) indicates CNB-CdLa2S4CNB and CdLa in composite photocatalyst2S4Two phases coexist.
Experimental example 2 ultraviolet-visible diffuse reflectance Spectroscopy analysis of sample
Comparative example 2 and CNB5And the ultraviolet-visible diffuse reflectance spectra of the products of examples 1-4, placing the samples into a sample cell, flattening the surface with a tabletting device, firstly checking with a blank reference, then characterizing each catalyst sample with an ultraviolet-visible diffuse reflectance spectrometer, and scanning the wavelength of 250-800 nm. The results are shown in FIG. 3.
In FIG. 3, (a) CdA2S4；(b)25％CNB-CdLa2S4；(c)50％CNB-CdLa2S4；(d)75％CNB-CdLa2S4；(e)80％CNB-CdLa2S4；(f)CNB5。
As can be seen from FIG. 3, the absorption wave of CNB is around 460nm, which can only absorb the waveLight having a length of 460nm or less, and therefore, the utilization efficiency of visible light is relatively low. And CNB5In contrast, CNB-CdLa2S4The absorption intensity of the composite photocatalyst in a 400-plus-800 nm visible light region is obviously enhanced, and the absorption wave also moves towards the long wave direction, which shows that CNB and CdLa2S4Synergistic effect may occur, so as to increase the light absorption range and light absorption intensity and make CNB-CdLa2S4The composite photocatalyst can more effectively utilize visible light, thereby being beneficial to enhancing the photocatalytic activity.
Experimental example 3 photoluminescence Spectroscopy of samples
Determination of CN, CNB5，CNB10，CNB15The photoluminescence spectrum of (a) is shown in fig. 4.
As can be seen from FIG. 4, all samples showed a strong emission peak at about 450nm with a fluorescence intensity of CNB15>CNB10>CN>CNB5Indicating CNB5The recombination degree of the photogenerated electron-hole pairs is minimum, and the separation degree of the electron-hole pairs is maximum. Thus CNB5The activity of (c) was highest. Therefore, when the composite photocatalyst is made, the CNB is selected5The boron-doped graphite phase carbon nitride part is compounded with the polymetallic sulfide.
Infrared spectroscopic analysis of sample of Experimental example 4
Determination of CN, CNB5，CNB10，CNB15And Fourier transform infrared spectrums of the products of the comparative example 2 and the examples 1 to 4 are shown in fig. 5 and 6.
FIG. 5 shows CN, CNB5，CNB10，CNB15Fourier transform infrared spectrogram;
FIG. 6 shows (a) Cdla2S4；(b)25％CNB-CdLa2S4；(c)50％CNB-CdLa2S4；(d)75％CNB-CdLa2S4；(e)80％CNB-CdLa2S4；(f)CNB5。
As can be seen from FIG. 5, the temperature at 3100--1The broader absorption peak at this point is the stretching mode of vibration of-NH-. Wherein the concentration is at 1240 and 1640cm-1Region(s)Internal absorption peak: 1240. 1320, 1400, 1430, 1570 and 1640cm-1Corresponding to carbon nitride aromatic-C-N-stretching vibration mode and-C-N-stretching vibration mode, wherein the length of the vibration mode is 810cm-1The absorption peak at (A) is the bending vibration mode of the 3-s-triazine ring.
As can also be seen from fig. 5, the ir spectra of CN and CNB are substantially identical, which indicates that CNB and CN are identical in structure and composition of the functional groups.
As can be seen from FIG. 6, 3100--1The broader absorption peaks at (A) are the stretching vibration modes of-NH-, of which 1240, 1320, 1400, 1430, 1570 and 1640cm-1The corresponding absorption peaks are C-N stretching vibration mode and C-N stretching vibration mode of carbon nitride aromatic, wherein the absorption peak is 810cm-1The absorption peak is the bending vibration mode of C-N-C. For pure CdLa2S4At 1610cm-1And 3420cm-1Peak value of (2) and CdA2S4The hydroxyl ions on the surface.
As can also be seen from FIG. 6, CNB-CdLa2S4The composite photocatalyst has the characteristic peak of CNB and CdLa2S4The characteristic peak of (A) indicates CNB-CdLa2S4The composite photocatalyst consists of CNB and CdLa2S4The two phases are composed, and are consistent with the detection result of XRD.
TEM and HR-TEM analysis of the samples of Experimental example 5
TEM (Transmission Electron microscopy) analysis of the products obtained in comparative example 2 and examples 1 to 4 was carried out using a CM200-FEG type transmission electron microscope (TEM, acceleration voltage 200kV, Philips Co.) and the results are shown in FIG. 7. Only d with HR-TEM is the aim to see the lattice fringes of the semiconductor.
In FIG. 7, (a) CdA2S4；(b)CNB5；(c)25％CNB-CdLa2S4；(d)80％CNB-CdLa2S4。
As shown in FIG. 7(a), CdLa2S4Mainly presents as a sphere; in FIG. 7(b), CNB is shown5Is a two-dimensional layered porous structure; 80% CNB-CdLa from FIG. 7(c)2S4As can be seen from the composite catalyst of (A), Cdla2S4The nano particles are dispersed on the surface of the CNB sheet layer; 80% CNB-CdLa of FIG. 7(d)2S4HR-TEM image of the composite catalyst shows CdLa2S4Has a interplanar spacing d of 0.293nm, corresponding to CdLa2S4The (300) plane of (2).
Experimental example 6 analysis of catalytic Activity of sample
Determination of CN, CNB5，CNB10，CNB15And the photocatalytic activity of the products of comparative example 2 and examples 1-4.
100mg of each catalyst sample was put into a 2-naphthol solution (50mL, 2X 10)-5mol/L), after adsorbing for 1h in a dark state, starting a 500W xenon lamp (lambda)>400nm), taking 4mL of suspension at regular intervals, centrifuging to remove the catalyst, measuring the change trend of the absorption spectrum of organic matters in the solution by using an ultraviolet-visible spectrometer, and evaluating the performance of the catalyst by using the degradation rate.
The degradation rate was calculated as W (%) - (A)0－At)/A0And (4) calculating the degradation rate by multiplying 100%, and drawing a visible light activity graph of different catalyst samples according to the obtained degradation rate. The results are shown in FIGS. 8 and 9.
In FIG. 8, (a) blank, (b) CN, (c) CNB15,(d)CNB10,(e)CNB5；
In FIG. 9, (a) CdA2S4；(b)25％CNB-CdLa2S4；(c)50％CNB-CdLa2S4；(d)75％CNB-CdLa2S4；(e)80％CNB-CdLa2S4；(f)CNB5。
As can be seen from FIG. 8, the dark reaction 2-naphthol hardly degrades, and CNB5The catalyst has better degradation effect than other catalysts, and the activity sequence is as follows: e.g. of the type>d>c>b>a, irradiating visible light for 4h under optimized conditions, and obtaining CNB5The degradation rate of 2-naphthol by photocatalysis reaches 58.9 percent.
As can be seen from FIG. 9, the dark reaction 2-naphthol hardly degraded; CNB-CdLa2S4The composite catalyst is obviously better than CNB5And Cdla2S4CatalysisThe degradation effect of the agent is good; with the mass percentage of CNB increasing, CNB-CdLa2S4The activity of the composite catalyst is firstly increased and then reduced, wherein when the mass percentage of CNB is 75%, 75% of CNB-CdLa2S4The activity of the composite catalyst is highest. Furthermore, 75% CNB-CdLa2S4After the photocatalytic reaction of the composite photocatalyst for 4 hours, 75 percent of CNB-CdLa2S4The degradation rate of 2-naphthol photocatalytic degradation medicine reaches 85.2 percent. The excellent performance is probably attributed to the fact that the appropriate amount of CNB promotes the composite photocatalyst CNB-CdLa2S4The effective separation of the photo-generated electron-hole pairs enhances the utilization rate of visible light.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A composite photocatalyst is characterized by comprising boron-doped graphite-phase carbon nitride and a metal sulfide.
2. The composite photocatalyst of claim 1, wherein the metal sulphide is a monometallic sulphide or a multimetallic sulphide, preferably a multimetallic sulphide.
3. The composite photocatalyst of claim 2, wherein the metal elements in the polymetallic sulfide are two of cadmium, lanthanum, terbium, europium, cerium, samarium and dysprosium, preferably cadmium and lanthanum.
4. The composite photocatalyst of claim 3, wherein the composite photocatalyst is CNB-CdLa2S4Preferably in the XRD pattern at 13.4 DEG, 17.66 DEG,Diffraction peaks appear at 23 °, 24.35 °, 26.48 °, 28.02 °, 30.45 °, 35.86 °, 42.94 °, 43.94 °, 46.78 °, 50.02 °, 53.46 °, 57.18 °, 60.88 °, 63.14 °, 68.06 °, 70.92 °, more preferably CdLa2S4Dispersed on the surface of the CNB sheet layer as nano-particles.
5. A method of preparing a composite photocatalyst, preferably a composite photocatalyst as claimed in any one of claims 1 to 4, comprising the steps of:
step 1, preparing boron-doped graphite-phase carbon nitride;
and 2, preparing the composite photocatalyst.
6. The method of claim 5, wherein step 1 comprises the steps of:
step 1-1, dissolving a carbon nitrogen source and a boron source in a solvent, and uniformly dispersing;
step 1-2, removing the solvent in the system in the step 1-1;
and 1-3, calcining, and performing post-treatment to obtain the boron-doped graphite-phase carbon nitride.
7. The method of claim 6, wherein in step 1-1, the carbon-nitrogen source is selected from the group consisting of melamine, cyanamide, urea; the boron source is selected from boron oxide, boric acid and sodium tetraphenylborate; the solvent is selected from distilled water, deionized water and purified water;
in the step 1-2, the temperature for removing the solvent is 70-90 ℃;
in the step 1-3, the calcination temperature is 450-650 ℃, and the post-treatment comprises cooling to room temperature and grinding.
8. The method of claim 5, wherein step 2 comprises the steps of:
step 2-1, dissolving the raw materials in a dispersing agent and uniformly mixing;
step 2-2, carrying out heat preservation reaction;
and 2-3, drying to obtain a final product.
9. The method of claim 8, wherein in step 2-1, the feedstock comprises a metal nitrate, a sulfur source, and boron-doped graphite phase carbon nitride; the dispersant is water, preferably distilled water, purified water and deionized water;
in the step 2-2, the temperature of the heat preservation reaction is 140-180 ℃;
in the step 2-3, the drying temperature is 50-70 ℃;
preferably, the first and second electrodes are formed of a metal,
in the step 2-1, the metal nitrate is selected from two of cadmium nitrate, lanthanum nitrate, terbium nitrate, europium nitrate, cerium nitrate, samarium nitrate and dysprosium nitrate; the sulfur source is selected from thiourea, ammonium thiocyanate and nitrothiocyanamide;
in the step 2-3, before drying, the system obtained in the step 2-2 is cooled to room temperature, then is centrifugally separated, and is washed by a solvent II.
10. Use of the composite photocatalyst according to any one of claims 1 to 4 or the composite photocatalyst prepared by the process according to any one of claims 5 to 9, for degrading contaminated wastewater, preferably wastewater containing phenols.
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