CN112206792A - Catalyst for heavy metal sewage treatment and preparation method thereof - Google Patents
Catalyst for heavy metal sewage treatment and preparation method thereof Download PDFInfo
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- CN112206792A CN112206792A CN202011140989.8A CN202011140989A CN112206792A CN 112206792 A CN112206792 A CN 112206792A CN 202011140989 A CN202011140989 A CN 202011140989A CN 112206792 A CN112206792 A CN 112206792A
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- Prior art keywords
- samarium
- bismuth
- ytterbium
- catalyst
- oxyiodide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 37
- 239000010865 sewage Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 53
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 53
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 claims abstract description 39
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 13
- -1 uranium ions Chemical class 0.000 claims abstract description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 20
- SBSSZSCMFDYICE-UHFFFAOYSA-N tetrabutylazanium;triiodide Chemical compound I[I-]I.CCCC[N+](CCCC)(CCCC)CCCC SBSSZSCMFDYICE-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 150000001621 bismuth Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 235000009518 sodium iodide Nutrition 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 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 5
- 150000001216 Samarium Chemical class 0.000 claims description 4
- 150000001225 Ytterbium Chemical class 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 claims description 3
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 3
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 claims description 3
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002496 iodine Chemical class 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 15
- 238000006722 reduction reaction Methods 0.000 abstract description 15
- 238000000746 purification Methods 0.000 abstract description 13
- 239000011651 chromium Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 8
- 229910052770 Uranium Inorganic materials 0.000 abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
-
- B01J35/39—
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
Abstract
The invention discloses a catalyst for heavy metal sewage treatment and a preparation method thereof. The catalyst is prepared by firstly preparing samarium and ytterbium codoped bismuth oxyiodide photocatalyst by a solvothermal method, then dispersing the samarium and ytterbium codoped bismuth oxyiodide photocatalyst into deionized water, and then addingAdding a certain amount of silicic acid, preparing the samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate composite photocatalyst by a hydrothermal method, and finally loading silver by a photo-reduction method to obtain the composite catalyst. The improvement of the performance of the photocatalyst is promoted by utilizing the synergistic effect of samarium and ytterbium, and the reduction purification capacity of the catalyst is improved by compounding with bismuth silicate to form a heterojunction and loading silver, so that the catalyst has more excellent treatment effect on hexavalent uranium ions (U) in heavy metal sewage6+) Hexavalent chromium ion (Cr)6+) The ability of (c); the preparation method of the catalyst is simple, and hexavalent uranium ions (U) in heavy metal wastewater are reduced6+) Hexavalent chromium ion (Cr)6+) Has good reduction and purification capability and is an ideal material for treating heavy metal sewage.
Description
Technical Field
The invention relates to the field of heavy metal sewage treatment, in particular to a catalyst for heavy metal sewage treatment and a preparation method thereof.
Background
With the rapid development of society, the discharge amount of industrial pollutants is increasing day by day, and serious pollution is caused to the ecological environment. Especially, heavy metal ions in the wastewater seriously damage the water ecological environment and cause great damage to aquatic animals, plants and human health. Therefore, the treatment of heavy metal ions in the wastewater has great significance for protecting the water ecological environment.
The problem of water environment pollution caused by heavy metal ions is not really solved all the time, and researchers explore methods for treating the heavy metal ion pollution in water, and the methods mainly comprise a physical remediation method, a chemical remediation method, a biological remediation method, a membrane separation technology, a semiconductor photocatalyst technology and the like. The photocatalyst technology is a new green technology, can remove organic pollutants and heavy metal ions in wastewater by using inexhaustible light energy, can solve the environmental problem and the energy problem simultaneously, and is paid attention by researchers in various countries.
Uranium is a typical heavy metal contaminant, which is chemically toxic and radioactive, presenting potential threats to the environment and human health. Uranium generally exists in a variety of chemical states, e.g. U0、U3+、U4+And U6+. U, the predominant chemical state in the environment being soluble6+And slightly soluble U4+Will be soluble U6+Reduction to slightly soluble U4+Is one of the important methods for removing radioactive contamination and recycling uranium. Log-C of Log-Hai et al3N4S, P doping modification is respectively carried out, and the modification is used as a photocatalyst to carry out UO2 2+And (4) degrading. Researches show that g-C is modified under the irradiation of a 350W xenon lamp (lambda is more than or equal to 420nm)3N4Photocatalytic reduction of UO2 2+Is more efficient than pure g-C3 N4. Wherein S is3-g-C3N4The material has optimal photocatalytic activity, and can treat UO within 20min2 2+The degradation rate of the catalyst is as high as 95 percent.
Chromium is a common heavy metal pollutant, Cr in water6+High toxicity and serious influence on human health, and Cr3+Much less toxic than Cr6+Thus, Cr is added6+Conversion to Cr3+Is an important means for removing chromium pollution and recycling chromium resources, and the semiconductor BiOI is loaded on g-C by Lishuangzhi and the like3N4Thereby forming BiOI/g-C3N4Composite effective for catalytic reduction of Cr6+When the BiOI loading was increased to 5% (mass fraction), the reduction rate reached a maximum of 97.2%.
Although the current research has achieved a great result, the photocatalytic reduction purification time of the photocatalyst is still long, and the preparation method is complex, so that the urgent need to develop a new photocatalyst capable of efficiently reducing and purifying heavy metals in wastewater still remains a problem which needs to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a catalyst for heavy metal sewage treatment and a preparation method thereof. The catalyst is prepared by firstly preparing samarium and ytterbium co-doped bismuth oxyiodide photocatalyst by a solvothermal method, then dispersing the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst into deionized water, then adding a certain amount of silicic acid, preparing the samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate composite photocatalyst by a hydrothermal method, and finally loading silver by a photo-reduction method to obtain the composite catalyst. The improvement of the performance of the photocatalyst is promoted by utilizing the synergistic effect of samarium and ytterbium, and the reduction purification capacity of the catalyst is improved by compounding with bismuth silicate to form a heterojunction and loading silver, so that the catalyst has more excellent treatment effect on hexavalent uranium ions (U) in heavy metal sewage6+) Hexavalent chromium ion (Cr)6+) (ii) a The preparation method of the catalyst is simple, and hexavalent uranium ions (U) in heavy metal wastewater are reduced6+) Hexavalent chromium ion (Cr)6+) Has good reduction and purification capability and is an ideal material for treating heavy metal sewage.
The invention adopts the following technical scheme:
a preparation method of a catalyst for heavy metal sewage treatment comprises the following steps:
(1) respectively weighing tetrabutylammonium triiodide and iodide, dissolving in 60-80 mL of ethanol, adding bismuth salt, and magnetically stirring for 1-4 h to form a solution A;
(2) weighing samarium salt, ytterbium salt and 0.001-0.003 mol of tetrabutylammonium triiodide in a certain proportion, dissolving in 30-40 mL of deionized water, and magnetically stirring to prepare a solution B;
(3) dropwise adding B into A under magnetic stirring, continuously stirring for 2-4 h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat at 140-160 ℃ for 12-16 h, centrifuging, washing and drying to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein, the doping amount of samarium is 1-2 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1-2 wt%;
(4) adding the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst prepared in the step (3) into deionized water, performing ultrasonic dispersion for 10-20 min, then adding a certain amount of silicic acid, performing ultrasonic dispersion for 20-30 min, then transferring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, performing constant-temperature reaction at 200-240 ℃ for 18-22 h, cooling to room temperature, filtering, washing and drying to obtain samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate; wherein the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.05-1: 0.10;
(5) taking a certain amount of samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate to ultrasonically disperse in 100mL of deionized water, adding a certain amount of silver nitrate solution, magnetically stirring for 40-60 min under the irradiation of a 450W xenon lamp, filtering, washing, and drying in vacuum to obtain the catalyst, wherein the loading amount of silver is 1-2 wt%.
Preferably, in step (1), the molar ratio of tetrabutylammonium triiodide to iodide salt is 1: 1.
Preferably, in the step (1), the molar ratio of tetrabutylammonium triiodide to bismuth salt is 1: 2.
Preferably, in step (1), the iodide salt is sodium iodide and/or potassium iodide; the bismuth salt is one or more of bismuth chloride, bismuth nitrate and bismuth acetate.
Preferably, in the step (2), the samarium salt is one or more of samarium chloride, samarium nitrate and samarium acetate; the ytterbium salt is one or more of ytterbium chloride, ytterbium nitrate and ytterbium acetate.
Preferably, in the step (2), the stirring speed is 200-300 rpm, and the stirring time is 0.5-2 h.
Preferably, in the step (3), the drying is carried out at 80-100 ℃ for 12-16 h.
Preferably, in the step (4), the drying is carried out at 80-100 ℃ for 10-14 h.
Preferably, in the step (5), the amount of the samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate is 0.2-0.4 g; the volume of the silver nitrate solution is 20-24 mL, and the concentration is 2.0 g/L.
The invention provides a catalyst prepared by the preparation method, wherein the catalyst is silver modified samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate, and the loading amount of silver is 1-2 wt%; the doping amount of samarium is 1-2 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1-2 wt%; the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.05-1: 0.10.
The catalyst for heavy metal sewage treatment and the preparation method thereof provided by the invention have the following technical effects:
(1) the samarium and ytterbium codoped bismuth oxyiodide photocatalyst is prepared by a solvothermal method, and the samarium and ytterbium codoped bismuth oxyiodide photocatalyst improves the crystal structure and the electronic structure of bismuth oxyiodide and further changes the energy band structure of the bismuth oxyiodide. By utilizing the synergistic effect of the two components, the reduction purification capability of the bismuth oxyiodide photocatalyst is obviously improved, the reduction efficiency of heavy metals is promoted, and the purification time is shortened.
(2) The tetrabutylammonium triiodide with small molecular weight is used as an organic iodine source, so that the formation of bismuth oxyiodide crystal form is promoted, the photocatalytic purification capability is promoted to be improved, and the reduction and purification of heavy metals are facilitated.
(3) The samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate composite photocatalyst is synthesized in situ, so that the preparation cost is saved, the bismuth silicate is generated in situ on the surface of the bismuth oxyiodide, and the composition of photo-generated electron-hole pairs is further inhibited by forming a heterojunction, so that the photocatalytic reduction capability is further improved.
(4) Silver is loaded by a photoreduction method, when the silver is deposited on the surface of the composite photocatalyst, electrons can be rapidly transmitted from the composite photocatalyst to the silver, and a space charge layer is formed between the silver and the composite photocatalyst, so that the recombination of photo-generated electrons and holes is further inhibited, the activity of the photocatalyst is further improved, and the reduction and purification of heavy metal sewage are further improved.
(5) The preparation method is simple and easy to control, and the prepared product has excellent performance and is beneficial to industrial production.
In conclusion, the catalyst for heavy metal sewage treatment prepared by the invention has excellent photocatalytic performance and excellent reduction and purification capacity for heavy metals in heavy metal sewage.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a catalyst for heavy metal sewage treatment comprises the following steps:
(1) weighing 2mmol of tetrabutylammonium triiodide and 2mmol of sodium iodide respectively, dissolving in 70mL of ethanol, adding 4mmol of bismuth nitrate, and magnetically stirring for 3h to form solution A;
(2) weighing samarium nitrate, ytterbium nitrate and 0.002mol of tetrabutylammonium triiodide in a certain proportion, and dissolving in 35mL of deionized water, wherein the rotating speed of magnetic stirring is 250rpm, and the stirring time is 1h, so as to form a solution B;
(3) dropwise adding B into A under magnetic stirring, continuously stirring for 3h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat for 14h at 150 ℃, centrifuging, washing, and drying for 14h at 90 ℃ to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein the doping amount of samarium is 1.5 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1.5 wt%;
(4) adding the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst prepared in the step (3) into deionized water, performing ultrasonic dispersion for 15min, then adding a certain amount of silicic acid, performing ultrasonic dispersion for 25min, then transferring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, performing constant-temperature reaction for 20h at 220 ℃, cooling to room temperature, filtering, washing, and drying for 12h at 90 ℃ to obtain samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate; wherein the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.08;
(5) taking 0.3g of samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate, ultrasonically dispersing the samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate in 100mL of deionized water, adding 22mL of silver nitrate solution with the concentration of 2.0g/L, magnetically stirring for 50min under the irradiation of a 450W xenon lamp, filtering, washing, and vacuum drying for 12h at 80 ℃ to obtain the catalyst, wherein the loading amount of silver is 1.5 wt%.
Example 2
A preparation method of a catalyst for heavy metal sewage treatment comprises the following steps:
(1) respectively weighing 2mmol of tetrabutylammonium triiodide and 2mmol of potassium iodide, dissolving in 80mL of ethanol, adding 4mmol of bismuth chloride, and magnetically stirring for 4h to form solution A;
(2) weighing samarium chloride, ytterbium acetate and 0.003mol of tetrabutylammonium triiodide in a certain proportion, dissolving in 40mL of deionized water, and preparing a solution B with the magnetic stirring rotation speed of 300rpm and the stirring time of 0.5 h;
(3) under magnetic stirring, dropwise adding B into A, continuously stirring for 4h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat at 160 ℃ for 12h, centrifuging, washing, and drying at 100 ℃ for 12h to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein, the doping amount of samarium is 2 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1 wt%;
(4) adding the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst prepared in the step (3) into deionized water, performing ultrasonic dispersion for 20min, then adding a certain amount of silicic acid, performing ultrasonic dispersion for 30min, then transferring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, performing constant-temperature reaction for 18h at 240 ℃, cooling to room temperature, filtering, washing, and drying for 10h at 100 ℃ to obtain samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate; wherein the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.10;
(5) taking 0.4g of samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate, ultrasonically dispersing the samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate in 100mL of deionized water, adding 24mL of silver nitrate solution with the concentration of 2.0g/L, magnetically stirring for 60min under the irradiation of a 450W xenon lamp, filtering, washing, and vacuum drying for 12h at 80 ℃ to obtain the catalyst, wherein the loading amount of silver is 2 wt%.
Example 3
A preparation method of a catalyst for heavy metal sewage treatment comprises the following steps:
(1) respectively weighing 2mmol of tetrabutylammonium triiodide and 2mmol of sodium iodide, dissolving in 60mL of ethanol, adding 4mmol of bismuth acetate, and magnetically stirring for 1h to form a solution A;
(2) weighing samarium acetate, ytterbium chloride and 0.001mol of tetrabutylammonium triiodide in a certain proportion, dissolving in 30mL of deionized water, and preparing a solution B with the magnetic stirring rotation speed of 200rpm and the stirring time of 2 h;
(3) under magnetic stirring, dropwise adding B into A, continuously stirring for 2h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat at 140 ℃ for 16h, centrifuging, washing, and drying at 80 ℃ for 16h to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein the doping amount of samarium is 1 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 2 wt%;
(4) adding the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst prepared in the step (3) into deionized water, performing ultrasonic dispersion for 10min, then adding a certain amount of silicic acid, performing ultrasonic dispersion for 20min, then transferring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, performing constant-temperature reaction for 22h at 200 ℃, cooling to room temperature, filtering, washing, and drying for 14h at 80 ℃ to obtain samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate; wherein the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.05;
(5) taking 0.2g of samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate to ultrasonically disperse in 100mL of deionized water, adding 20mL of silver nitrate solution with the concentration of 2.0g/L, magnetically stirring for 40min under the irradiation of a 450W xenon lamp, filtering, washing, and vacuum drying for 12h at 80 ℃ to obtain the catalyst, wherein the loading amount of silver is 1 wt%.
Comparative example 1
The procedure and conditions were the same as in example 1 except that tetrabutylammonium triiodide was not added.
Comparative example 2
Samarium was doped only in an amount of 3 wt%, and other steps and conditions were the same as in example 1.
Comparative example 3
Ytterbium was doped only in an amount of 3 wt%, and other steps and conditions were the same as in example 1.
Comparative example 4.
The doping was not performed and other steps and conditions were the same as in example 1.
Comparative example 5
A preparation method of a catalyst for heavy metal sewage treatment comprises the following steps:
(1) weighing 2mmol of tetrabutylammonium triiodide and 2mmol of sodium iodide respectively, dissolving in 70mL of ethanol, adding 4mmol of bismuth nitrate, and magnetically stirring for 3h to form solution A;
(2) weighing samarium nitrate, ytterbium nitrate and 0.002mol of tetrabutylammonium triiodide in a certain proportion, and dissolving in 35mL of deionized water, wherein the rotating speed of magnetic stirring is 250rpm, and the stirring time is 1h, so as to form a solution B;
(3) dropwise adding B into A under magnetic stirring, continuously stirring for 3h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat for 14h at 150 ℃, centrifuging, washing, and drying for 14h at 90 ℃ to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein the doping amount of samarium is 1.5 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1.5 wt%;
(4) taking 0.3g of samarium and ytterbium codoped bismuth oxyiodide photocatalyst, ultrasonically dispersing the samarium and ytterbium codoped bismuth oxyiodide photocatalyst in 100mL of deionized water, adding 22mL of silver nitrate solution with the concentration of 2.0g/L, magnetically stirring for 50min under the irradiation of a 450W xenon lamp, filtering, washing, and vacuum drying for 12h at 80 ℃ to obtain the catalyst, wherein the loading amount of silver is 1.5 wt%.
Comparative example 6
A preparation method of a catalyst for heavy metal sewage treatment comprises the following steps:
(1) weighing 2mmol of tetrabutylammonium triiodide and 2mmol of sodium iodide respectively, dissolving in 70mL of ethanol, adding 4mmol of bismuth nitrate, and magnetically stirring for 3h to form solution A;
(2) weighing samarium nitrate, ytterbium nitrate and 0.002mol of tetrabutylammonium triiodide in a certain proportion, and dissolving in 35mL of deionized water, wherein the rotating speed of magnetic stirring is 250rpm, and the stirring time is 1h, so as to form a solution B;
(3) dropwise adding B into A under magnetic stirring, continuously stirring for 3h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat for 14h at 150 ℃, centrifuging, washing, and drying for 14h at 90 ℃ to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein the doping amount of samarium is 1.5 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1.5 wt%;
(4) adding the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst prepared in the step (3) into deionized water, performing ultrasonic dispersion for 15min, then adding a certain amount of silicic acid, performing ultrasonic dispersion for 25min, then transferring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, performing constant-temperature reaction for 20h at 220 ℃, cooling to room temperature, filtering, washing, and drying for 12h at 90 ℃ to obtain samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate; wherein the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.08.
The photocatalysts of examples 1 to 3 and comparative examples 1 to 6 were used for experiments of heavy metal wastewater treatment. The specific method comprises the following steps:
10mg of photocatalyst was added to 15mL of 200mg/L Cr (VI) (K)2Cr2O7) Adjusting pH to 3 in the solution, stirring in the dark for 15min,then, the mixture was stirred under irradiation with a xenon lamp (350W) equipped with a 420nm filter, and the purification rate at 15min was measured.
10mg of photocatalyst is added into 15mL of 200mg/L U (VI) solution, the pH value is adjusted to 4, stirring is carried out for 15min under the dark condition, then stirring is carried out under the irradiation of a xenon lamp (350W) with a 420nm optical filter, and the degradation rate is measured for 15 min.
Specific test results are shown in table 1:
through comparison between the above examples 1-3 and the comparative examples 1-6, the catalyst of the present invention has good reduction and purification capability to Cr (VI) and U (VI) in heavy metal wastewater, and the treatment time is short, and due to the mutual synergistic effect of the components, the catalyst of the present invention is an ideal material for treating heavy metal wastewater.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for heavy metal sewage treatment is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively weighing tetrabutylammonium triiodide and iodide, dissolving in 60-80 mL of ethanol, adding bismuth salt, and magnetically stirring for 1-4 h to form a solution A;
(2) weighing samarium salt, ytterbium salt and 0.001-0.003 mol of tetrabutylammonium triiodide in a certain proportion, dissolving in 30-40 mL of deionized water, and magnetically stirring to prepare a solution B;
(3) dropwise adding B into A under magnetic stirring, continuously stirring for 2-4 h, transferring to a polytetrafluoroethylene high-pressure reaction kettle, preserving heat at 140-160 ℃ for 12-16 h, centrifuging, washing and drying to obtain a samarium and ytterbium co-doped bismuth oxyiodide photocatalyst; wherein, the doping amount of samarium is 1-2 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1-2 wt%;
(4) adding the samarium and ytterbium co-doped bismuth oxyiodide photocatalyst prepared in the step (3) into deionized water, performing ultrasonic dispersion for 10-20 min, then adding a certain amount of silicic acid, performing ultrasonic dispersion for 20-30 min, then transferring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, performing constant-temperature reaction at 200-240 ℃ for 18-22 h, cooling to room temperature, filtering, washing and drying to obtain samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate; wherein the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.05-1: 0.10;
(5) taking a certain amount of samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate to ultrasonically disperse in 100mL of deionized water, adding a certain amount of silver nitrate solution, magnetically stirring for 40-60 min under the irradiation of a 450W xenon lamp, filtering, washing, and drying in vacuum to obtain the catalyst, wherein the loading amount of silver is 1-2 wt%.
2. The method of claim 1, wherein: in the step (1), the molar ratio of tetrabutylammonium triiodide to the iodide salt is 1: 1.
3. The method of claim 1, wherein: in the step (1), the molar ratio of tetrabutylammonium triiodide to bismuth salt is 1: 2.
4. The method of claim 1, wherein: in the step (1), the iodine salt is sodium iodide and/or potassium iodide; the bismuth salt is one or more of bismuth chloride, bismuth nitrate and bismuth acetate.
5. The method of claim 1, wherein: in the step (2), the samarium salt is one or more of samarium chloride, samarium nitrate and samarium acetate; the ytterbium salt is one or more of ytterbium chloride, ytterbium nitrate and ytterbium acetate.
6. The method of claim 1, wherein: in the step (2), the stirring speed is 200-300 rpm, and the stirring time is 0.5-2 h.
7. The method of claim 1, wherein: in the step (3), the drying is carried out at 80-100 ℃ for 12-16 h.
8. The method of claim 1, wherein: in the step (4), the drying is carried out at 80-100 ℃ for 10-14 h.
9. The method of claim 1, wherein: in the step (5), the amount of samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate is 0.2-0.4 g; the volume of the silver nitrate solution is 20-24 mL, and the concentration is 2.0 g/L.
10. A catalyst prepared according to the process of any one of claims 1 to 9, characterized in that: the catalyst is silver-modified samarium and ytterbium co-doped bismuth oxyiodide/bismuth silicate, wherein the loading amount of silver is 1-2 wt%; the doping amount of samarium is 1-2 wt% relative to the mass of bismuth oxyiodide; the doping amount of ytterbium is 1-2 wt%; the molar ratio of bismuth oxyiodide to bismuth silicate is 1: 0.05-1: 0.10.
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| CN114950499A (en) * | 2022-03-11 | 2022-08-30 | 深圳信息职业技术学院 | Preparation method and application of bimetallic Co and Ce composite bismuth-based photocatalytic material |
| CN115710019A (en) * | 2022-11-15 | 2023-02-24 | 东华理工大学 | Method for reducing hexavalent uranium by photocatalysis and application |
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