CN113477241B - Ternary composite photocatalyst and preparation method and application thereof - Google Patents
Ternary composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113477241B CN113477241B CN202111042260.1A CN202111042260A CN113477241B CN 113477241 B CN113477241 B CN 113477241B CN 202111042260 A CN202111042260 A CN 202111042260A CN 113477241 B CN113477241 B CN 113477241B
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- composite photocatalyst
- holmium
- erbium
- scandium
- ytterbium
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- 239000011206 ternary composite Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 239000002096 quantum dot Substances 0.000 claims abstract description 33
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 30
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 29
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 29
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 29
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZGZFTXZUXCTNLE-UHFFFAOYSA-N [Yb].[Nb] Chemical compound [Yb].[Nb] ZGZFTXZUXCTNLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- -1 amide compound Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 241000257465 Echinoidea Species 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- GYUURHMITDQTRU-UHFFFAOYSA-N tributyl(pyridin-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CC=N1 GYUURHMITDQTRU-UHFFFAOYSA-N 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- 238000010884 ion-beam technique Methods 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000000917 Erbium Chemical class 0.000 claims description 4
- 150000000922 Holmium Chemical class 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003325 scandium Chemical class 0.000 claims description 4
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 claims 1
- 241000700605 Viruses Species 0.000 claims 1
- 230000000593 degrading effect Effects 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 22
- 239000002253 acid Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
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- 230000000694 effects Effects 0.000 description 25
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- 238000012360 testing method Methods 0.000 description 25
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 22
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 20
- 230000005291 magnetic effect Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000011449 brick Substances 0.000 description 10
- 229960003405 ciprofloxacin Drugs 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910052724 xenon Inorganic materials 0.000 description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- PVDVPOZEJCXUAM-UHFFFAOYSA-N acetonitrile;n,n-diethylethanamine Chemical compound CC#N.CCN(CC)CC PVDVPOZEJCXUAM-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
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- 238000011081 inoculation Methods 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229940047889 isobutyramide Drugs 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- GNWIIFNEOUYUPD-UHFFFAOYSA-N O.[Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.[Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GNWIIFNEOUYUPD-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- NBSLDXHEXGYVEP-UHFFFAOYSA-N erbium(3+) trinitrate hydrate Chemical compound O.[Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O NBSLDXHEXGYVEP-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- HZQULVNEUCEVQV-UHFFFAOYSA-N scandium(3+);trinitrate;hydrate Chemical compound O.[Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HZQULVNEUCEVQV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XIOPWXFTXDPBEY-UHFFFAOYSA-N ytterbium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XIOPWXFTXDPBEY-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WCWXGMCOMKXIGP-UHFFFAOYSA-N [Sc].[Er] Chemical compound [Sc].[Er] WCWXGMCOMKXIGP-UHFFFAOYSA-N 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 230000006798 recombination Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/20—Vanadium, niobium or tantalum
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Abstract
The invention discloses a ternary composite photocatalyst and a preparation method and application thereof. The ternary composite photocatalyst is prepared by mixing porous graphene, ytterbium niobium oxysalt and holmium, scandium and erbium three-metal quantum dots, and then performing ball milling and calcination. The preparation method of the ternary composite photocatalyst comprises the following steps: 1) preparing porous graphene; 2) preparing ytterbium niobic acid salt; 3) preparing holmium, scandium and erbium trimetal quantum dots; 4) and mixing the porous graphene, the ytterbium niobium oxysalt and the holmium, scandium and erbium three-metal quantum dots, carrying out ball milling, and calcining to obtain the ternary composite photocatalyst. The ternary composite photocatalyst has excellent light stability and good photocatalytic effect, does not need to adopt a sacrificial agent or a photoadjuvant in the application process, and is clean, energy-saving and environment-friendly.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a ternary composite photocatalyst and a preparation method and application thereof.
Background
The photocatalytic technology is a green technology which realizes the functions of purifying pollutants, synthesizing substances, converting substances and the like on the basis of the oxidation-reduction capacity of a photocatalyst under the condition of illumination. In general, a photocatalytic oxidation reaction uses a semiconductor as a catalyst and light as energy to degrade organic substances into carbon dioxide and water. Therefore, the photocatalysis technology is an efficient and safe environment-friendly environmental purification technology and has important application prospect in the fields of energy and environment.
The photocatalyst is the key of the photocatalytic technology, and the performance of the photocatalyst plays a decisive role in determining whether the photocatalytic technology can realize practical application. At present, most of common photocatalysts have obvious defects, and are difficult to completely meet the requirements of practical application, and the defects are specifically shown in the following aspects: 1) the photocatalyst is easy to generate photoproduction electron-hole pair recombination, the electron transmission efficiency is low, and the photocatalytic effect is poor; 2) in the application process of the photocatalyst, a sacrificial agent or an auxiliary catalyst is mostly needed to improve the photocatalytic effect, the cost is high, and secondary pollution is easily caused; 3) the composite photocatalyst has weak interaction among the components, poor stability and poor actual photocatalytic effect.
Therefore, the development of a photocatalyst with excellent light stability and good photocatalytic effect is of great significance for realizing large-scale practical application of photocatalytic technology.
Disclosure of Invention
The invention aims to provide a ternary composite photocatalyst and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the three-element composite photocatalyst is prepared by mixing porous graphene, ytterbium niobium oxysalt and holmium, scandium and erbium metal quantum dots, and then performing ball milling and calcination.
Preferably, the mass ratio of the porous graphene to the holmium-scandium-erbium three-metal quantum dots is 3: 1.6-2.4: 0.8-1.2.
Preferably, the particle size of the holmium, scandium and erbium trimetal quantum dot is 3 nm-8 nm.
Preferably, the specific operation of the calcination is as follows: heating to 200-600 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 10-15 h, heating to 1000-1200 ℃ at a heating rate of 8-12 ℃/min, applying a pressure of 80-100 MPa, and preserving heat and pressure for 20-30 h.
The preparation method of the ternary composite photocatalyst comprises the following steps:
1) crushing the sea urchin shells, freeze-drying, carbonizing, stripping with variable-frequency infrasonic waves, and performing energy-carrying ion beam-focused ion beam etching to obtain porous graphene;
2) will K7HNb6O19Ytterbium nitrate, sodium carbonate, lithium phosphate, 3-amino-1, 2, 4-triazole and 2-tri-n-butylstannyl pyridine are dispersed by adding water and subjected to microwave reaction to obtain ytterbium niobium oxysalt;
3) adding water to disperse soluble holmium salt, soluble scandium salt and soluble erbium salt, adding an amide compound and an aliphatic amine compound, and carrying out hydrothermal reaction to obtain holmium, scandium and erbium trimetal quantum dots;
4) and mixing the porous graphene, the ytterbium niobium oxysalt and the holmium, scandium and erbium three-metal quantum dots, carrying out ball milling, and calcining to obtain the ternary composite photocatalyst.
Preferably, the sea urchin shells in the step 1) are crushed, pressed into a square brick shape, and then freeze-dried.
Preferably, the freeze-drying in step 1) is carried out at-200 ℃ to-50 ℃.
Preferably, the carbonization in step 1) is carried out at 1500 to 2000 ℃.
Preferably, the frequency of the variable frequency infrasound wave in the step 1) is 4 Hz-7 Hz.
Preferably, K in step 2)7HNb6O19The preparation method comprises the following steps: mixing Nb with2O5Mixing with KOH according to the molar ratio of 1:1, ball milling, calcining, naturally cooling, dissolving the calcined product in water, and recrystallizing to obtain the crystal water-containing K7HNb6O19。
Preferably, K in step 2)7HNb6O19The molar ratio of ytterbium nitrate to sodium carbonate to lithium phosphate to 3-amino-1, 2, 4-triazole to 2-tri-n-butylstannyl pyridine is 1: 2.6-3.0: 1.0-4.5: 2.6-4.0: 2.0-4.9: 1.5-2.8.
Preferably, the microwave reaction in the step 2) is carried out at 200-250 ℃, and the reaction time is 10-15 h.
Preferably, the molar ratio of the soluble holmium salt, the soluble scandium salt, the soluble erbium salt, the amide compound and the aliphatic amine compound in the step 3) is 1: 1.0-1.9: 1.9-5.0: 1.5-7.9.
Preferably, the amide compound in step 3) is at least one of isobutyramide, acetamide, butyramide, thioacetamide and allylthiourea.
Preferably, the aliphatic amine compound in step 3) is at least one of triethylamine, diethylamine, triethanolamine, dibutylamine and diisopropylamine.
Preferably, the hydrothermal reaction in the step 3) is carried out at 180-220 ℃, and the reaction time is 12-24 h.
The invention has the beneficial effects that: the ternary composite photocatalyst is prepared by compounding porous graphene, ytterbium niobate oxometallate and holmium, scandium and erbium metal quantum dots, has excellent light stability and good photocatalysis effect, does not need to adopt a sacrificial agent or a photoadjuvant in the application process, and is clean, energy-saving and environment-friendly.
Specifically, the method comprises the following steps:
1) the three-element composite photocatalyst is a magnetic interface photocatalyst, and when the three-element composite photocatalyst is placed in a magnetic field, the electron transmission efficiency can be remarkably improved by utilizing the regulation and control of interface magnetic resistance and electron cyclotron resonance, so that the photocatalysis effect is improved;
2) the ternary composite photocatalyst can be converted into a substance with paramagnetic property from a non-ferromagnetic substance (diamagnetism) under a fixed magnetic field, and provides a foundation for wide industrial application of photocatalysis;
3) the porous graphene in the ternary composite photocatalyst is prepared from waste sea urchin shells, so that waste is changed into valuable, the structure of the material is changed in a nanoscale by using an energy-carrying ion-focused ion beam FIB carving combined technology through effects of irradiation damage, sputtering and the like, and a nano-level porous channel is introduced by directly irradiating three-dimensional few-layer graphene, so that the specific surface area is increased, the photocatalytic activity sites are increased, and the efficient and stable photocatalytic effect is finally achieved;
4) the ternary composite photocatalyst does not need to adopt a sacrificial agent or an auxiliary catalyst in the application process, so that secondary pollution is avoided, and meanwhile, a good photocatalytic effect can be achieved;
5) the ternary composite photocatalyst has a unique three-dimensional graphene framework and an ytterbium niobic acid salt (polyoxometallate) framework, and a coupling effect exists between the two frameworks, so that the composition of holmium, scandium and erbium three-metal quantum dots is facilitated, and the excellent light stability and the excellent photocatalytic effect are both considered.
Drawings
Fig. 1 is an SEM image of porous graphene in example 1.
Fig. 2 is a TEM image of porous graphene in example 1.
Fig. 3 is a raman spectrum of the porous graphene in example 1.
Fig. 4 is a graph showing the specific surface area test results of the porous graphene in example 1.
Fig. 5 is a TEM image of the holmium, scandium, and erbium trimetallic quantum dot in example 1.
FIG. 6 is a photocurrent graph of the three-way composite photocatalyst of example 1 under the condition of an additional standing magnetic field and without the additional standing magnetic field.
FIG. 7 is a graph of electrochemical impedance of the three-way composite photocatalyst of example 1 with and without an additional resting magnetic field.
FIG. 8 is a graph showing the effect of the photo cycle endurance test on the three-way composite photocatalyst of example 1.
Fig. 9 is a diagram illustrating the photocatalytic degradation effect of the porous graphene, the ytterbium niobic acid salt, the holmium, scandium and erbium three-metal quantum dots, the porous graphene-ytterbium niobic acid salt-holmium, scandium and erbium three-metal quantum dot mixture and the ternary composite photocatalyst on ciprofloxacin in sewage in example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of the ternary composite photocatalyst comprises the following steps:
1) cleaning, drying and crushing sea urchin shells, pressing the sea urchin shells into square bricks, placing the square bricks at the temperature of-150 ℃ for freeze drying for 60min, carbonizing at the temperature of 1800 ℃ for 720min, placing the square bricks in variable frequency infrasonic waves with the frequency of 4 Hz-7 Hz for 360min for stripping, and performing energy-carrying ion beam-focused ion beam etching for 15min to obtain porous graphene (marked as 3D graphene);
2) mixing Nb with2O5Mixing with KOH according to the molar ratio of 1:1, ball-milling for 30min, calcining for 1h at 1100 ℃ in a muffle furnace, naturally cooling, dissolving the calcined product in 60mL of deionized water, and recrystallizing to obtain K containing crystal water7HNb6O191mmol of K7HNb6O19Dispersing 2mmol of ytterbium nitrate pentahydrate, 3mmol of sodium carbonate, 3mmol of lithium phosphate, 3mmol of 3-amino-1, 2, 4-triazole and 2.8mmol of 2-tri-n-butylstannyl pyridine in 80mL of water, carrying out microwave reaction at 230 ℃ for 12h, centrifuging, washing a product obtained by centrifuging for 6 times by using an ethanol solution (the volume ratio of ethanol to deionized water is 1: 1), and carrying out vacuum drying for 72h to obtain ytterbium niobic acid salt;
3) dispersing 1mmol of holmium nitrate hydrate, 1mmol of scandium nitrate hydrate and 1.9mmol of erbium nitrate hydrate in 60mL of deionized water, carrying out ultrasonic treatment for 30min, adding 2mmol of isobutyramide and 7.9mmol of triethylamine, adding the reaction mixed solution into a stainless steel autoclave, heating to 200 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation for 12h, naturally cooling to room temperature, centrifuging, washing the product obtained by centrifuging for 4 times with deionized water, and carrying out freeze drying for 12h at-30 ℃ to obtain holmium-scandium-erbium trimetal quantum dots;
4) mixing porous graphene, ytterbium, niobium, oxometallate and holmium, scandium and erbium three-metal quantum dots according to a mass ratio of 3:2:1, adding the mixture into a planetary ball mill, carrying out ball milling for 60min, placing the ball mill into a tube furnace, introducing helium, heating to 200 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 12h, rotating a quartz test tube of the tube furnace at 360 DEG at a rotating speed of 30r/min, heating to 1100 ℃ at a heating rate of 10 ℃/min, applying a pressure of 80MPa, and keeping the temperature and the pressure for 24h to obtain the ternary composite photocatalyst.
And (3) performance testing:
1) the Scanning Electron Microscope (SEM) image, the Transmission Electron Microscope (TEM) image, the raman spectrum image, and the specific surface area test result image of the porous graphene in step 1) of this example are shown in fig. 1, fig. 2, and fig. 3, respectively.
As can be seen from fig. 1 and 2: the porous graphene obtained in the step 1) has the structural characteristic of few layers and multiple pores, the number of layers is less than 5, and the lattice spacing is 0.34 nm.
As can be seen from fig. 3: the porous graphene obtained in the step 1) has a good crystal form.
As can be seen from fig. 4: the specific surface area of the porous graphene obtained in the step 1) is large and is as high as 4238.10m2/g。
2) A TEM image of the holmium, scandium and erbium trimetallic quantum dot of step 2) of this example is shown in fig. 5.
As can be seen from fig. 5: the particle size of the holmium, scandium and erbium trimetallic quantum dots in the step 2) is about 4nm, and the particle size is uniform.
3) The photocurrent graph of the three-way composite photocatalyst of the embodiment under the condition of the additional standing magnetic field and the condition without the additional standing magnetic field is shown in fig. 6.
As can be seen from fig. 6: the construction of the magnetic interface in the three-way composite photocatalyst of the embodiment is beneficial to the separation of photo-generated electrons and holes, can obviously improve the photo-generated current density, and shows excellent photocatalytic effect.
4) The electrochemical impedance spectrum of the three-way composite photocatalyst of the embodiment under the condition of the additional static magnetic field and the condition without the additional static magnetic field is shown in FIG. 7.
As can be seen from fig. 7: the construction of the magnetic interface in the three-way composite photocatalyst of the embodiment is beneficial to the separation of photo-generated electrons and holes, and shows excellent photocatalytic effect.
5) The effect graph of the light cycle endurance test of the three-way composite photocatalyst of the embodiment in the presence of the static magnetic field and in the absence of the static magnetic field is shown in fig. 8.
As can be seen from fig. 8: the three-way composite photocatalyst of the embodiment has excellent stability and durability.
6) The photocatalytic degradation effects of the three-element composite photocatalyst on different pollutants in sewage are shown in the following table:
TABLE 1 photocatalytic degradation effect of three-way composite photocatalyst on different pollutants in sewage
Note:axenon lamp (wavelength lambda)>420nm）。
As can be seen from Table 1: the three-way composite photocatalyst (with the magnetic interface) of the embodiment has excellent photocatalytic degradation effect on various pollutants in sewage.
7) The photocatalytic degradation effect of the three-way composite photocatalyst and the common photocatalyst on ciprofloxacin (100 mg/L) in sewage in the embodiment is shown in the following table:
TABLE 2 ternary composite photocatalyst and common photocatalyst for photocatalytic degradation of ciprofloxacin in sewage
Note:axenon lamp (wavelength lambda)>420nm）；bThe photocatalytic degradation efficiency of the degraded substance is monitored every 2h, and the cycle is repeated.
As can be seen from Table 2: compared with various traditional photocatalysts, the ternary composite photocatalyst provided by the embodiment has the advantages that the photocatalytic degradation effect on ciprofloxacin in sewage is obviously improved, and the light stability is better.
8) The photocatalytic degradation effect of the three-way composite photocatalyst and the common photocatalyst of the embodiment on escherichia coli (100 mg/L) in sewage is shown in the following table:
TABLE 3 photocatalytic degradation effect of ternary composite photocatalyst and common photocatalyst on Escherichia coli in sewage
Note:axenon lamp (wavelength lambda)>420nm）；bThe photocatalytic degradation efficiency of the degraded substance is monitored every 2h, and the cycle is repeated.
As can be seen from Table 3: compared with various traditional photocatalysts, the three-element composite photocatalyst has the advantages that the photocatalytic degradation effect on escherichia coli in sewage is remarkably improved, and the light stability is better.
9) The photocatalytic degradation effect of the three-way composite photocatalyst and the common photocatalyst of the embodiment on H1N1 virus (100 mg/L) in sewage is shown in the following table:
TABLE 4 photocatalytic degradation effect of ternary composite photocatalyst and common photocatalyst on H1N1 virus in sewage
Note:axenon lamp (wavelength lambda)>420nm）；bThe photocatalytic degradation efficiency of the degraded substance is monitored every 2h, and the cycle is repeated.
As can be seen from Table 4: compared with various traditional photocatalysts, the three-element composite photocatalyst provided by the embodiment has the advantages that the photocatalytic degradation effect on H1N1 virus in sewage is remarkably improved, and the light stability is better.
10) The graph of the photocatalytic degradation effect of the porous graphene, the ytterbium niobate, the holmium scandium erbium trimetal quantum dot, the porous graphene-ytterbium niobate-holmium scandium erbium trimetal quantum dot mixture (simply mixed according to the mass ratio of 3:2: 1) and the ternary composite photocatalyst on ciprofloxacin (100 mg/L) in sewage in the embodiment is shown in fig. 9.
As can be seen from fig. 9: when the porous graphene, ytterbium niobate oxometallate and holmium, scandium and erbium three-metal quantum dots are independently used as the photocatalyst, the photocatalytic degradation effect on ciprofloxacin in sewage is poor; when the porous graphene, ytterbium niobate and holmium, scandium and erbium three-metal quantum dots are simply mixed to be used as a photocatalyst, the photocatalytic degradation effect on ciprofloxacin in sewage is poor, and the effect is inferior to that when the porous graphene, ytterbium niobate or holmium, scandium and erbium three-metal quantum dots are used alone; the porous graphene, ytterbium niobium oxysalt and holmium, scandium and erbium three-metal quantum dots are mixed and then are subjected to ball milling and calcination, so that a better effect can be achieved, and when the porous graphene, ytterbium niobium oxysalt and holmium, scandium and erbium three-metal quantum dots are used as a photocatalyst, the photocatalytic degradation effect on ciprofloxacin in sewage is very excellent.
11) Taking a xenon lamp with the power of 300W as a light source, taking 60mL of printing and dyeing mill sewage (COD =375mg/L, BOD =423mg/L, both COD and BOD greatly exceed GB/T11914-: a chromatographic column: c18250 mm X4.6 mm (5 μm); mobile phase: 0.05mol/L phosphoric acid solution/triethylamine-acetonitrile (82: 18), flow rate: 0.8 mL/min; detection wavelength: a fluorescence detector with an excitation wavelength of 280 nm; emission wavelength 450 nm; sample introduction amount: 20 muL, performing photolysis for 6h, testing COD according to a dichromate method for determining chemical oxygen demand of water quality GB/T11914 and 1989, adopting a CTL-12 type COD rapid tester, testing BOD according to a method for determining dilution and inoculation of biochemical oxygen demand (BOD 5) of water quality GB/T7488 and 1987, and adopting an OXITop BOD tester.
Tests show that after the three-way composite photocatalyst is treated, the COD of the sewage of the printing and dyeing mill is 11mg/L, the BOD is 2mg/L, and both the COD and the BOD reach the GB/T11914-.
12) A xenon lamp with the power of 300W is used as a light source, 60mL of paper mill sewage (COD =621mg/L, BOD =598mg/L, both COD and BOD greatly exceed GB/T11914-: a chromatographic column: c18250 mm X4.6 mm (5 μm); mobile phase: 0.05mol/L phosphoric acid solution/triethylamine-acetonitrile (82: 18), flow rate: 0.8 mL/min; detection wavelength: a fluorescence detector with an excitation wavelength of 280 nm; emission wavelength 450 nm; sample introduction amount: 20 muL, performing photolysis for 6h, testing COD according to a dichromate method for determining chemical oxygen demand of water quality GB/T11914 and 1989, adopting a CTL-12 type COD rapid tester, testing BOD according to a method for determining dilution and inoculation of biochemical oxygen demand (BOD 5) of water quality GB/T7488 and 1987, and adopting an OXITop BOD tester.
Tests show that after the ternary composite photocatalyst is treated, the COD of the sewage of the paper mill is 16mg/L, the BOD is 3mg/L, and both the COD and the BOD reach the GB/T11914-.
13) A xenon lamp with the power of 300W is used as a light source, 60mL of urban refuse landfill leachate (COD =532mg/L, 653=653mg/L, COD and BOD both greatly exceed GB/T11914-: a chromatographic column: c18250 mm X4.6 mm (5 μm); mobile phase: 0.05mol/L phosphoric acid solution/triethylamine-acetonitrile (82: 18), flow rate: 0.8 mL/min; detection wavelength: a fluorescence detector with an excitation wavelength of 280 nm; emission wavelength 450 nm; sample introduction amount: 20 muL, performing photolysis for 6h, testing COD according to a dichromate method for determining chemical oxygen demand of water quality GB/T11914 and 1989, adopting a CTL-12 type COD rapid tester, testing BOD according to a method for determining dilution and inoculation of biochemical oxygen demand (BOD 5) of water quality GB/T7488 and 1987, and adopting an OXITop BOD tester.
Tests show that after the ternary composite photocatalyst is treated, the COD of the leachate of the municipal refuse landfill is 15mg/L, the BOD is 2mg/L, and both the COD and the BOD reach the GB/T11914-.
14) A xenon lamp with the power of 300W is used as a light source, 60mL of hospital sewage (COD =875mg/L, BOD =521mg/L, both COD and BOD greatly exceed GB/T11914-: a chromatographic column: c18250 mm X4.6 mm (5 μm); mobile phase: 0.05mol/L phosphoric acid solution/triethylamine-acetonitrile (82: 18), flow rate: 0.8 mL/min; detection wavelength: a fluorescence detector with an excitation wavelength of 280 nm; emission wavelength 450 nm; sample introduction amount: 20 muL, performing photolysis for 6h, testing COD according to a dichromate method for determining chemical oxygen demand of water quality GB/T11914 and 1989, adopting a CTL-12 type COD rapid tester, testing BOD according to a method for determining dilution and inoculation of biochemical oxygen demand (BOD 5) of water quality GB/T7488 and 1987, and adopting an OXITop BOD tester.
Tests show that after the ternary composite photocatalyst is treated, the COD of the hospital sewage is 18mg/L, the BOD is 5mg/L, and both the COD and the BOD reach the GB/T11914-.
15) A xenon lamp with the power of 300W is used as a light source, 60mL of ditch domestic sewage (COD =421mg/L, BOD =498mg/L, both COD and BOD greatly exceed GB/T11914-: a chromatographic column: c18250 mm X4.6 mm (5 μm); mobile phase: 0.05mol/L phosphoric acid solution/triethylamine-acetonitrile (82: 18), flow rate: 0.8 mL/min; detection wavelength: a fluorescence detector with an excitation wavelength of 280 nm; emission wavelength 450 nm; sample introduction amount: 20 muL, performing photolysis for 6h, testing COD according to a dichromate method for determining chemical oxygen demand of water quality GB/T11914 and 1989, adopting a CTL-12 type COD rapid tester, testing BOD according to a method for determining dilution and inoculation of biochemical oxygen demand (BOD 5) of water quality GB/T7488 and 1987, and adopting an OXITop BOD tester.
Tests show that after the ternary composite photocatalyst is treated, the COD of the domestic sewage in the ditch is 13mg/L, the BOD is 6mg/L, and both the COD and the BOD reach the GB/T11914-.
Example 2:
a preparation method of the ternary composite photocatalyst comprises the following steps:
1) cleaning, drying and crushing sea urchin shells, pressing the sea urchin shells into square bricks, placing the square bricks at-100 ℃ for freeze drying for 120min, carbonizing at 1600 ℃ for 360min, placing the square bricks in variable frequency infrasonic waves with the frequency of 4 Hz-7 Hz for 720min for stripping, and performing energy-carrying ion beam-focused ion beam etching for 5min to obtain porous graphene;
2) mixing Nb with2O5Mixing with KOH according to the molar ratio of 1:1, ball-milling for 30min, calcining for 1h at 1100 ℃ in a muffle furnace, naturally cooling, dissolving the calcined product in 100mL of deionized water, and recrystallizing to obtain K containing crystal water7HNb6O191mmol of K7HNb6O19Dispersing 3mmol of ytterbium nitrate pentahydrate, 4mmol of sodium carbonate, 3mmol of lithium phosphate, 2mmol of 3-amino-1, 2, 4-triazole and 2.8mmol of 2-tri-n-butylstannyl pyridine in 100mL of water, carrying out microwave reaction at 230 ℃ for 12h, centrifuging, washing a product obtained by centrifuging for 6 times by using an ethanol solution (the volume ratio of ethanol to deionized water is 1: 1), and carrying out vacuum drying for 72h to obtain ytterbium niobic acid salt;
3) dispersing 1mmol of holmium nitrate hydrate, 1.5mmol of scandium nitrate hydrate and 1.9mmol of erbium nitrate hydrate in 30mL of deionized water, carrying out ultrasonic treatment for 30min, adding 3mmol of isobutyramide and 7.9mmol of triethylamine, adding the reaction mixed solution into a stainless steel autoclave, heating to 200 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation for 12h, naturally cooling to room temperature, centrifuging, washing the product obtained by centrifuging for 4 times with deionized water, and carrying out freeze drying for 12h at-10 ℃ to obtain holmium, scandium and erbium trimetal quantum dots;
4) mixing porous graphene, ytterbium, niobium, oxometallate and holmium, scandium and erbium three-metal quantum dots according to a mass ratio of 3:2:1, adding the mixture into a planetary ball mill, carrying out ball milling for 60min, placing the ball mill into a tube furnace, introducing helium, heating to 200 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 12h, rotating a quartz test tube of the tube furnace at 360 DEG at a rotating speed of 30r/min, heating to 1100 ℃ at a heating rate of 10 ℃/min, applying a pressure of 80MPa, and keeping the temperature and the pressure for 24h to obtain the ternary composite photocatalyst.
Through tests, the micro-morphology of the three-way composite photocatalyst of the embodiment is highly similar to that of the three-way composite photocatalyst of the embodiment 1, and the light stability and the photocatalytic effect are very close to those of the three-way composite photocatalyst of the embodiment 1 (for example, the photocatalytic degradation effect of the three-way composite photocatalyst of the embodiment on ciprofloxacin under the same conditions is 5 min/98.5%).
Example 3:
a preparation method of the ternary composite photocatalyst comprises the following steps:
1) cleaning, drying and crushing sea urchin shells, pressing the sea urchin shells into square bricks, placing the square bricks at-200 ℃ for freeze drying for 30min, carbonizing at 2000 ℃ for 120min, placing the square bricks in variable frequency infrasonic waves with the frequency of 4 Hz-7 Hz for 120min for stripping, and performing energy-carrying ion beam-focused ion beam etching for 120min to obtain porous graphene;
2) mixing Nb with2O5Mixing with KOH according to the molar ratio of 1:1, ball-milling for 30min, calcining for 1h at 1100 ℃ in a muffle furnace, naturally cooling, dissolving the calcined product in 200mL of deionized water, and recrystallizing to obtain K containing crystal water7HNb6O191mmol of K7HNb6O19Dispersing 2.7mmol of ytterbium nitrate pentahydrate, 3mmol of sodium carbonate, 3.1mmol of lithium phosphate, 2.8mmol of 3-amino-1, 2, 4-triazole and 2.8mmol of 2-tri-n-butylstannyl pyridine in 200mL of water, carrying out microwave reaction at 230 ℃ for 12h, centrifuging, washing a product obtained by centrifuging for 6 times by using an ethanol solution (the volume ratio of ethanol to deionized water is 1: 1), and carrying out vacuum drying for 72h to obtain ytterbium niobium oxysalt;
3) dispersing 1mmol of holmium nitrate hydrate, 1.8mmol of scandium nitrate hydrate and 1.9mmol of erbium nitrate hydrate in 200mL of deionized water, carrying out ultrasonic treatment for 30min, adding 4mmol of isobutyramide and 7.9mmol of triethylamine, adding the reaction mixed solution into a stainless steel autoclave, heating to 200 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation for 12h, naturally cooling to room temperature, centrifuging, washing the product obtained by centrifuging for 4 times with deionized water, and carrying out freeze drying for 12h at-20 ℃ to obtain holmium, scandium and erbium trimetal quantum dots;
4) mixing porous graphene, ytterbium, niobium, oxometallate and holmium, scandium and erbium three-metal quantum dots according to a mass ratio of 3:2:1, adding the mixture into a planetary ball mill, carrying out ball milling for 60min, placing the ball mill into a tube furnace, introducing helium, heating to 200 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 12h, rotating a quartz test tube of the tube furnace at 360 DEG at a rotating speed of 30r/min, heating to 1100 ℃ at a heating rate of 10 ℃/min, applying a pressure of 80MPa, and keeping the temperature and the pressure for 24h to obtain the ternary composite photocatalyst.
Through tests, the micro-morphology of the three-way composite photocatalyst of the embodiment is highly similar to that of the three-way composite photocatalyst of the embodiment 1, and the light stability and the photocatalytic effect are very close to those of the three-way composite photocatalyst of the embodiment 1 (for example, the photocatalytic degradation effect of the three-way composite photocatalyst of the embodiment on ciprofloxacin under the same conditions is 5 min/99.5%).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A three-element composite photocatalyst is characterized in that: the ternary composite photocatalyst is prepared by mixing porous graphene, ytterbium niobium oxysalt and holmium, scandium and erbium three-metal quantum dots, and then performing ball milling and calcination; the mass ratio of the porous graphene to the ytterbium niobate oxyniobate to the holmium, scandium and erbium-containing trimetal quantum dots is 3: 1.6-2.4: 0.8-1.2; the specific operation of the calcination is as follows: firstly heating to 200-600 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 10-15 h, then heating to 1000-1200 ℃ at a heating rate of 8-12 ℃/min, simultaneously applying a pressure of 80-100 MPa, preserving heat and maintaining pressure for 20-30 h; the calcination is carried out in a helium atmosphere.
2. The three-way composite photocatalyst of claim 1, wherein: the particle size of the holmium, scandium and erbium trimetal quantum dot is 3-8 nm.
3. The method for preparing the three-element composite photocatalyst as claimed in claim 1 or 2, which is characterized by comprising the following steps:
1) crushing the sea urchin shells, freeze-drying, carbonizing, stripping with variable-frequency infrasonic waves, and performing energy-carrying ion beam-focused ion beam etching to obtain porous graphene;
2) will K7HNb6O19Ytterbium nitrate, sodium carbonate, lithium phosphate, 3-amino-1, 2, 4-triazole and 2-tri-n-butylstannyl pyridine are dispersed by adding water and subjected to microwave reaction to obtain ytterbium niobium oxysalt;
3) adding water to disperse soluble holmium salt, soluble scandium salt and soluble erbium salt, adding an amide compound and an aliphatic amine compound, and carrying out hydrothermal reaction to obtain holmium, scandium and erbium trimetal quantum dots;
4) and mixing the porous graphene, the ytterbium niobium oxysalt and the holmium, scandium and erbium three-metal quantum dots, carrying out ball milling, and calcining to obtain the ternary composite photocatalyst.
4. The method for preparing the three-element composite photocatalyst as claimed in claim 3, wherein: step 1), the freeze drying is carried out at-200 to-50 ℃; the carbonization in the step 1) is carried out at 1500-2000 ℃; the frequency of the frequency-conversion infrasonic waves in the step 1) is 4 Hz-7 Hz.
5. The preparation method of the three-way composite photocatalyst as claimed in claim 3 or 4, wherein: step 2) said K7HNb6O19Ytterbium nitrate, sodium carbonate, lithium phosphate, 3-amino-1, 2, 4-triazole and 2-tri-n-butylstannyl pyridine in a molar ratio of 1: 2.6-3.0: 1.0-4.5: 2.6-4.0: 2.0-4.9: 1.5-2.8; the microwave reaction in the step 2) is carried out at the temperature of 200-250 ℃, and the reaction time is 10-15 h.
6. The preparation method of the three-way composite photocatalyst as claimed in claim 3 or 4, wherein: step 3), the molar ratio of the soluble holmium salt, the soluble scandium salt, the soluble erbium salt, the amide compound and the aliphatic amine compound is 1: 1.0-1.9: 1.9-5.0: 1.5-7.9; the hydrothermal reaction in the step 3) is carried out at 180-220 ℃, and the reaction time is 12-24 h.
7. Use of the three-way composite photocatalyst of claim 1 or 2 for degrading organic pollutants, bacteria and viruses.
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