CN113019454A - NH (hydrogen sulfide)2Preparation method and application of-MIL-101 (Fe) @ NiCoP composite nano photocatalyst - Google Patents
NH (hydrogen sulfide)2Preparation method and application of-MIL-101 (Fe) @ NiCoP composite nano photocatalyst Download PDFInfo
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- CN113019454A CN113019454A CN202110235854.8A CN202110235854A CN113019454A CN 113019454 A CN113019454 A CN 113019454A CN 202110235854 A CN202110235854 A CN 202110235854A CN 113019454 A CN113019454 A CN 113019454A
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 58
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 5
- 238000000034 method Methods 0.000 title description 5
- 239000004098 Tetracycline Substances 0.000 claims abstract description 45
- 229960002180 tetracycline Drugs 0.000 claims abstract description 45
- 229930101283 tetracycline Natural products 0.000 claims abstract description 45
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 9
- 231100000719 pollutant Toxicity 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 230000003115 biocidal effect Effects 0.000 claims abstract description 4
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 8
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 abstract description 4
- 229940088710 antibiotic agent Drugs 0.000 abstract description 4
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 32
- 238000006731 degradation reaction Methods 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- 239000002086 nanomaterial Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PSVSZBOMJGAVRS-UHFFFAOYSA-N 2,3-diaminoterephthalic acid Chemical compound NC1=C(N)C(C(O)=O)=CC=C1C(O)=O PSVSZBOMJGAVRS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
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- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the technical field of preparation and application of nano photocatalytic materials, and particularly relates to NH2-MIL-101(Fe) @ NiCoP nano photocatalyst and its preparation method and application, the preparation method is: by FeCl3·6H2O、NH2Preparation of NH from-BDC and DMF2-MIL-101 (Fe); reacting NH2‑MIL‑101(Fe) dispersed in CoCl by in-situ deposition2·6H2Preparation of NH in a mixed solution of O and RP2-MIL-101(Fe) @ NiCoP composite nano photocatalyst. NH prepared by the invention2Application of-MIL-101 (Fe) @ NiCoP nano photocatalyst in degrading antibiotic pollutants in water, such as organic pollutants of tetracycline and the like. NH obtained according to the invention2the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst shows high-efficiency photocatalytic activity, has a good application prospect in the aspect of removing pollutants such as antibiotics in water by visible light, and is simple in preparation method, economical and feasible.
Description
Technical Field
The invention belongs to the technical field of preparation and application of nano photocatalytic materials, and particularly relates to NH2-MIL-101(Fe) @ NiCoP nano photocatalyst and its preparation method and application.
Background
With the development of socioeconomic, the pollution problem of trace and trace antibiotics in water is a great concern for researchers. At present, methods such as adsorption, membrane treatment, biological oxidation, catalytic degradation and the like are all applied to the removal of antibiotics in water. Among them, the method for removing antibiotics in water by visible light catalytic degradation of nano materials is popular among researchers due to the high utilization efficiency of visible light and no secondary pollution.
In the photocatalytic material, in order to facilitate the transmission of electrons, active nano materials such as metals and metal oxides are generally compounded with matrix nano materials such as graphene oxide, carbon nanotubes and metal framework materials, so as to obtain a composite nano material with better photocatalytic performance. However, many of the host materials have a narrow light absorption range, and cannot fully utilize visible light, so that the visible light degradation efficiency of the nano materials is low. Meanwhile, many active nano materials are precious metals and compounds, so that the cost of the photocatalytic nano material is greatly increased. Researches show that the adoption of a proper cocatalyst can expand the visible light absorption range of the matrix nano material, effectively promote the separation of holes and photo-generated electrons and reduce the photocatalytic overpotential of the catalyst. Transition metal phosphide is a novel cocatalyst, which is composed of a transition metal and phosphorus element, and has recently received attention from researchers. The transition metal phosphide has the advantages of no toxicity, low cost, high natural abundance and the like, and is an ideal choice for realizing high-efficiency photocatalytic degradation of pollutants. Phosphides have become excellent catalysts for replacing noble metals. Research shows that NiCoP has lower over potential and charge transfer resistance and electrochemical performance superior to that of single metal phosphide.
Disclosure of Invention
It is an object of the present invention to provide NH2The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst comprises the following steps:
s1 by FeCl3·6H2O (ferric chloride hexahydrate), NH2Preparation of NH from-BDC (diaminoterephthalic acid) and DMF (N, N-dimethylformamide)2-MIL-101(Fe)；
S2, adding NH2-MIL-101(Fe) dispersed in NiCl by in situ deposition2·6H2O (Nickel chloride hexahydrate), CoCl2·6H2Preparation of NH from a mixed solution of O (cobalt chloride hexahydrate) and RP (red phosphorus)2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst;
said S1 includes
S101, FeCl3·6H2O and NH2-BDC dissolved in DMF to give a homogeneous mixed solution;
s102, pouring the mixed solution into a polytetrafluoroethylene reaction kettle for heating reaction;
s103, cooling after heating reaction, cleaning with a first cleaning agent, and drying to obtain NH2-MIL-101(Fe)。
In the step S102, the heating temperature is 110 ℃, and the reaction time is 20-28 h.
In the step S103, the first cleaning agent is dimethylformamide and methanol, and the cleaning mode is a mode of alternately cleaning the dimethylformamide and the methanol.
Said S2 includes
S201, adding NH2-MIL-101(Fe) is added to the alcohol-water mixed solution to form a homogeneous suspension;
s202, mixing NiCl2·6H2O and CoCl2·6H2Adding O into the suspension for dissolving to form a mixed solution A;
s203, adding RP, Cetyl Trimethyl Ammonium Bromide (CTAB) and Sodium Dodecyl Benzene Sulfonate (SDBS) into the mixed solution A to form a mixed solution B;
s204, heating the mixed solution B in a reaction kettle for reaction;
s205 heating, reacting, cooling, cleaning with a second cleaning agent, and drying to obtain NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
In S201, the volume ratio of the alcohol-water mixed solution is VAlcohol(s)：VWater (W)＝1:1。
In S202, NiCl2·6H2O and CoCl2·6H2The molar ratio of O is 1: 30.
In the step S204, the heating temperature is 110 ℃, and the reaction time is 20-28 h;
in 205, the second cleaning agent is water and ethanol, and the cleaning mode is a mode of alternately cleaning with water and ethanol.
Another object of the present invention is to provide a NH2Application of-MIL-101 (Fe) @ NiCoP nano photocatalyst, namely NH2Application of-MIL-101 (Fe) @ NiCoP nano photocatalyst in degrading antibiotic pollutants in water, such as organic pollutants of tetracycline and the like.
Has the advantages that:
(1) the invention selects NH2MIL-101(Fe) as support, using NH2The hierarchical pore structure of MIL-101(Fe) and the threshold limiting effect of the nanometer pore channel can improve the dispersity of the noble metal NiCoP-like nanometer particles, increase the specific surface area, increase the active center of the photocatalytic reaction and finally improve the photocatalytic performance. At the same time, NH2MIL-101(Fe) can be used for immobilizing photocatalysis, so that the recovery and the recycling of the photocatalyst are facilitated, and secondary pollution is avoided;
(2) the invention adopts an in-situ deposition method to prepare NH in situ2-MIL-101(Fe) @ NiCoP composite nano photocatalyst, Tetracycline (TC) is used as a simulated pollutant to evaluate the photocatalytic performance of the obtained sample, and NH is investigated under the influence of different TC pollutant concentrations, the adding amount of the photocatalytic material, the pH of the solution, the ionic strength and other factors in the solution2Degradation effect of-MIL-101 (Fe) @ NiCoP composite nano photocatalyst on TCThe effect of the fruit. The results showed 10mg of NH2The degradation efficiency of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst on TC with the concentration of 50mg/L of 50mL reaches more than 90 percent within 2 hours;
(3) the composite nano photocatalyst prepared by the invention has good stability, and the degradation efficiency is still more than 80% after the composite nano photocatalyst is repeatedly used for 4 times. The degradation mechanism research shows that O2-And the electron hole is the main active species for degrading TC, with the final degradation product being H2O and CO2。
Drawings
FIG. 1 is NH2-Scanning Electron Microscopy (SEM) and elemental analysis (eai) images of MIL-101(Fe) @ NiCoP composite nanophotocatalyst;
FIG. 2 is NH2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst X-ray photoelectron spectroscopy (XPS);
FIG. 3 is NH2MIL-101(Fe) and NH2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst fourier-infrared absorption spectrum (FT-IR);
FIG. 4 is NH2MIL-101(Fe) and NH2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst solid uv absorption spectrum (DRS);
FIG. 5 is NH2MIL-101(Fe) and NH2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst time-resolved fluorescence spectrogram (PL);
FIG. 6(A) is the TC concentration in the solution, 6(B) is NH in water2-MIL-101(Fe) @ NiCoP composite nano photocatalyst dosage, 6(C) is solution pH value, 6(D) is NH under different conditions of solution ionic strength and the like2-MIL-101(Fe) @ NiCoP composite nano photocatalyst influences TC degradation efficiency.
FIG. 7 shows the reactive group vs. NH in the reaction2-MIL-101(Fe) @ NiCoP composite nano photocatalyst influences the TC removal effect in the solution.
Detailed Description
In order to make the technical means, creation features, achievement objects and effects of the invention easy to understand, a novel NH of the invention is described below with reference to the accompanying drawings2-MIL-101(Fe) @ NiCoP complexThe preparation method of the synthetic nano photocatalyst and the specific description of the degradation of the tetracycline visible light in water are provided.
The invention adopts a solvothermal method and an in-situ deposition method to prepare NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
The first step is FeCl3·6H2O、NH2Preparing NH by using-BDC and DMF as raw materials through a solvothermal method2-MIL-101(Fe) nanomaterial. The second step is to subject the prepared NH2-MIL-101(Fe) NPs dispersed in NiCl2·6H2O、CoCl2·6H2Preparing NH by in-situ deposition in mixed solution of O and RP2-MIL-101(Fe) @ NiCoP composite nano photocatalyst. The third step is to take antibiotic pollutant TC in the water solution as a research object and investigate NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst has TC removing effect under visible light radiation.
Example 1
NH2The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst comprises the following steps:
NH2preparation of MIL-101(Fe)
Accurately weighing 0.675g FeCl3·6H2Dissolving O and 15mL of DMF in ultrasonic; then, 0.225g of NH was added to the mixed solution2BDC, transferring the mixture to a polytetrafluoroethylene reaction kettle after ultrasonic dissolution, heating the mixture to 110 ℃ in an oven, and reacting for 24 hours; naturally cooling to room temperature, repeatedly and alternately washing with DMF and methanol for multiple times, and vacuum drying at 60 deg.C for 2-6h to obtain NH2-MIL-101(Fe) nanomaterial.
NH2Preparation of-MIL-101 (Fe) @ NiCoP composite nano photocatalyst
Accurately weigh 0.2g NH2MIL-101(Fe) nanomaterial, added to 50mL (V)Alcohol(s)：VWater (W)1:1), ultrasonically dispersing to form uniform suspension; adding 0.05mmoL of NiCl2·6H2CoCl of O and 1.5mmoL2·6H2Adding O into the suspension, stirring and dissolving; subsequently, 25mmoL of Red Phosphorus (RP),0.1g of CTAB and 0.1g of SDBS were added to the above mixed solution and stirred at ordinary temperatureDissolving for 30 min; transferring the mixed solution into a reaction kettle, and reacting the mixed solution with the mixed solution at 200 ℃ for 24 hours; naturally cooling to room temperature, repeatedly and alternately washing with water and ethanol for multiple times, and vacuum drying at 60 deg.C for 2-6h to obtain NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
FIG. 1(A) shows NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nano photocatalyst in scanning electron microscope. As shown in FIG. 1(A), NiCoP was successfully deposited on NH2-MIL-101(Fe) nanomaterial surface; FIGS. 1(B), (C), (D), (E), (F), (G) and (H) are NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst elemental analysis plot; fig. 1(B), (C), (D), (E), (F), (G) and (H) show the distribution of C, N, O, Fe, Ni, Co and P elements, respectively, and it can be seen that the distribution of C, N, O, Fe, Ni, Co and P elements in the material is relatively uniform. Successful preparation of NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
FIGS. 2(A), (B), (C), (D), (E), (F), (G) and (H) are NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nano photocatalyst X-ray photoelectron spectroscopy (XPS). FIGS. 2(A), (B), (C), (D), (E), (F), (G) and (H) show XPS spectra of C, N, O, Fe, Ni, Co and P elements, respectively, and XPS characterization proves that NH is successfully prepared2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
FIG. 3 shows NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP nanocomposite Fourier Infrared absorption Spectroscopy (FT-IR). 3342.088 and 3411.514cm in the figure-1The peaks in the green and green boxes belong to NH2-a characteristic absorption peak of MIL-101 (Fe); the characteristic peaks in the blue circle belong to the Ni-P and Co-P bonds on NiCoP. It can be seen from the figure that NiCoP is successfully loaded on NH2-MIL-101(Fe) nanomaterial surface.
FIG. 4 shows NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst solid uv absorption spectrum; after NiCoP modification, NH2The absorption wavelength range of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is 200-700 nm, and the intensity is obviously higher than that of NH2-MIL-101(Fe)。
FIG. 5 shows NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nano photocatalyst time-resolved fluorescence spectrogram; the photoluminescence intensity comes from the recombination of free carriers in the nanocomposite. Therefore, a decrease in fluorescence intensity means that the material has a higher carrier separation efficiency. As shown in FIG. 4, NH2MIL-101(Fe) @ NiCoP has a specific NH ratio2Lower luminescence intensity of MIL-101 (Fe). This phenomenon accounts for NH2The carrier separation capacity of-MIL-101 (Fe) @ NiCoP is higher, which is more beneficial to the photodegradation of tetracycline.
Example 2
Photocatalytic degradation TC experiment
2-40 mg of NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst is added into 50mL of TC aqueous solution with the newly configured concentration range of 10-300 mg/L, and the mixture is placed into a photochemical reactor and stirred for 30min at room temperature in a dark place to reach adsorption balance. Then, turning on a light source, irradiating the solution by a 300w xenon lamp, sampling every 30min to measure absorbance, and obtaining the solubility C of the TC solution by using a standard curve, wherein the initial concentration of TC is set as C0 according to the formula: (1-C/C0) 100%, the degradation efficiency (R) of TC was calculated.
Researches NH (hydrogen sulfide) under different conditions of TC pollutant concentration, material addition, solution pH value, ionic strength and the like in different catalytic reaction times2Effect of-MIL-101 (Fe) @ NiCoP composite nanophotocatalyst on TC degradation effect, as shown in fig. 6.
FIG. 6A shows 10mg NH at different TC contaminant concentrations2-MIL-101(Fe) @ NiCoP composite nano photocatalyst influences the degradation effect of TC. As can be seen from FIG. 6A, when the TC concentration in the water is 10-120 mg/L, NH is present2The degradation efficiency of the MIL-101(Fe) @ NiCoP composite nano photocatalyst on tetracycline in water is increased along with the increase of the concentration of the tetracycline; NH when the concentration of tetracycline in water is higher than 120mg/L2The degradation efficiency of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst on tetracycline in water is reduced along with the increase of the concentration of the tetracycline.
FIG. 6B shows 2-40 mg of NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst for 50mg/mL T in 50mL solutionThe effect of removal efficiency of C; the results show that with NH2Increase of dosage of-MIL-101 (Fe) @ NiCoP composite nano photocatalytic material, NH2The degradation efficiency of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst on TC in water is gradually improved.
FIG. 6C is the pH of the solution versus NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst effect on TC removal in water; the results show that at natural pH, NH2The degradation efficiency of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst to tetracycline in water is highest.
FIG. 6D is the ionic strength in solution versus NH in example 1 of the invention2-MIL-101(Fe) @ NiCoP composite nanophotocatalyst effect on tetracycline elimination in water; the results show that the change of ionic strength in water is to NH2the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst has no obvious influence on the degradation efficiency of TC in water.
FIG. 7 shows reactive groups in reaction to NH in example 1 of the present invention2-MIL-101(Fe) @ NiCoP composite nano photocatalyst influences the TC removal effect in water. As can be seen from FIG. 7, NH in the absence of any quencher2The removal rate of-MIL-101 (Fe) @ NiCoP composite nano photocatalyst to TC can reach 91.0%. The photodegradation efficiency of TC under visible light was reduced to 84.5% after 10.0mM IPA was added to the solution. When 10.0mM AO was added, the photodegradation efficiency of TC dropped to 53.7%. When 5.0mM of 1,4-BQ was added, the degradation efficiency of TC was significantly reduced to only 21.6%. The results show that OH contributes to the degradation of TC, but is not the main active species in the photocatalytic process, and h+As the main active ingredient, participate in the degradation of TC, and at the same time, O2-Is the most dominant active species of photocatalytic TC.
As can be seen from example 2, when 10mg of NH were added2-MIL-101(Fe) @ NiCoP composite nano photocatalyst is added into 50mL of 50mg/mL TC solution, and 2h, NH are radiated under visible light condition2The degradation efficiency of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst on TC can reach 91.0%.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. NH (hydrogen sulfide)2The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is characterized by comprising the following steps:
s1 by FeCl3·6H2O、NH2Preparation of NH from-BDC and DMF2-MIL-101(Fe)；
S2, adding NH2-MIL-101(Fe) dispersed in NiCl by in situ deposition2·6H2O、CoCl2·6H2Preparation of NH in a mixed solution of O and RP2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
2. NH according to claim 12-MIL-101(Fe) @ NiCoP composite nano photocatalyst and its preparation method, characterized in that, S1 includes
S101, FeCl3·6H2O and NH2-BDC dissolved in DMF to give a homogeneous mixed solution;
s102, pouring the mixed solution into a polytetrafluoroethylene reaction kettle for heating reaction;
s103, cooling after heating reaction, cleaning with a first cleaning agent, drying,to obtain NH2-MIL-101(Fe)。
3. NH according to claim 22The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is characterized in that in S102, the heating temperature is 110 ℃, and the reaction time is 20-28 h.
4. NH according to claim 22The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is characterized in that in S103, a first cleaning agent is dimethylformamide and methanol, and the cleaning mode is a mode of alternately cleaning the dimethylformamide and the methanol.
5. NH according to claim 12-MIL-101(Fe) @ NiCoP composite nano photocatalyst and its preparation method, characterized in that, S2 includes
S201, adding NH2-MIL-101(Fe) is added to the alcohol-water mixed solution to form a homogeneous suspension;
s202, mixing NiCl2·6H2O and CoCl2·6H2Adding O into the suspension for dissolving to form a mixed solution A;
s203, adding RP, CTAB and SDBS into the mixed solution A to form a mixed solution B;
s204, heating the mixed solution B in a reaction kettle for reaction;
s205 heating, reacting, cooling, cleaning with a second cleaning agent, and drying to obtain NH2-MIL-101(Fe) @ NiCoP composite nano photocatalyst.
6. NH according to claim 52The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is characterized in that in S201, the volume ratio of an alcohol-water mixed solution is VAlcohol(s)：VWater (W)＝1:1。
7. NH according to claim 52-MIL-101(Fe) @ NiCoP composite nano photocatalyst preparation method, its special feature isCharacterized in that in S202, NiCl2·6H2O and CoCl2·6H2The molar ratio of O is 1: 30.
8. NH according to claim 52The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is characterized in that in S204, the heating temperature is 110 ℃, and the reaction time is 20-28 h.
9. NH according to claim 52The preparation method of the-MIL-101 (Fe) @ NiCoP composite nano photocatalyst is characterized in that in 205, the second cleaning agent is water and ethanol, and the cleaning mode is a mode of alternately cleaning the water and the ethanol.
10. NH (hydrogen sulfide)2-MIL-101(Fe) @ NiCoP nano photocatalyst, which is characterized in that: NH (NH)2Application of-MIL-101 (Fe) @ NiCoP nano photocatalyst in degrading antibiotic pollutants in water, such as organic pollutants of tetracycline and the like.
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