CN110227516B - ZnIn2S4/BiPO4Heterojunction photocatalyst, preparation method and application thereof - Google Patents
ZnIn2S4/BiPO4Heterojunction photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 26
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 claims abstract description 24
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 20
- 230000015556 catabolic process Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 13
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 12
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 11
- 235000018417 cysteine Nutrition 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000001488 sodium phosphate Substances 0.000 claims description 10
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 230000002349 favourable effect Effects 0.000 abstract description 6
- -1 nitrate ions Chemical class 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000001788 irregular Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 241000482268 Zea mays subsp. mays Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/39—
-
- B01J35/613—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
Disclosed herein are ZnIn2S4/BiPO4p-n heterojunction photocatalyst, preparation method and application thereof, and ZnIn2S4/BiPO4The specific surface area of the p-n heterojunction photocatalyst is 87.3458m2·g‑1Pore volume of 0.223cm3·g‑1(ii) a The ZnIn2S4/BiPO4The preparation raw materials of the p-n heterojunction photocatalyst are nano spherical bismuth phosphate and indium zinc sulfide, the particle size of the nano spherical bismuth phosphate is 80-150 nm, and the specific surface area of the nano spherical bismuth phosphate is 5.3011m2·g‑1Pore volume of 0.022cm3·g‑1. The method is simple to operate, economical and environment-friendly, and templates such as surfactants and the like are not required to be added in the preparation process. And, ZnIn2S4/BiPO4The p-n heterojunction photocatalyst exhibits a specific ZnIn ratio2S4And BiPO4The single catalytic performance has high photocatalytic activity, the specific surface area and the pore volume of the material are obviously improved, and the large specific surface area is favorable for adsorbing more nitrate ions during photocatalysis and is favorable for improving the photocatalytic activity of the heterojunction photocatalyst.
Description
Technical Field
The invention belongs to the field of water resource protection, and relates to ZnIn2S4/BiPO4A heterojunction photocatalyst, a preparation method and an application thereof, in particular to TypeII nIn2S4/BiPO4Heterojunction photocatalyst, preparation method and application thereof.
Background
High-concentration nitrate in drinking water has potential harm to human health, and semiconductor photocatalysis technology is widely researched due to the advantages of high efficiency, energy conservation, thorough pollutant degradation and the like, and is a water treatment method for removing nitrate in water by using semiconductor materials such as zinc oxide, titanium dioxide, zirconium oxide and the like as catalysts under the induction of ultraviolet light. The technology is characterized in that the semiconductor photocatalyst is used for generating photoproduction electrons-holes with higher oxidation reduction capability under the irradiation of a specific light source to realize the efficient degradation elimination of organic pollutants, and the technology is widely applied due to the advantages of high degradation efficiency, short period, low cost and the like. The preparation method of the existing photocatalyst comprises the following steps: the sol-gel method is a method for obtaining the required oxide by calcining metal organic or inorganic compounds after the processes of solution, sol, gel and the like, and has the advantages of uniform components, controllable composition, higher purity and the like, but generally the obtained nano powder is easy to agglomerate.
BiPO4(bismuth phosphate) as a novel photocatalyst has a good effect of photocatalytic degradation of organic pollutants under ultraviolet light, and is widely concerned due to low price, convenient preparation and no toxicity. And BiPO4Is a wide forbidden band material, has weak response to visible light, low light energy utilization rate and low photocatalytic activity under visible light, and seriously limits BiPO4The use of (1).
Disclosure of Invention
Aiming at the existing BiPO4The invention aims to provide ZnIn with weak response to visible light, low light energy utilization rate, low photocatalytic activity under visible light and the like2S4/BiPO4A p-n heterojunction photocatalyst, a preparation method and application thereof.
In order to solve the problems, the invention adopts the technical scheme that:
ZnIn2S4/BiPO4p-n heterojunction photocatalyst, the ZnIn2S4/BiPO4The specific surface area of the p-n heterojunction photocatalyst is 87.3458m2·g-1Pore volume of 0.223cm3·g-1；
The ZnIn2S4/BiPO4The preparation raw materials of the p-n heterojunction photocatalyst are nano spherical bismuth phosphate and indium zinc sulfide, the particle size of the nano spherical bismuth phosphate is 80-150 nm, and the specific surface area of the nano spherical bismuth phosphate is 5.3011m2·g-1Pore volume of 0.022cm3·g-1。
Further, the specific surface area of the indium zinc sulfide is 100.0427m2·g-1Pore volume of 0.206cm3·g-1。
ZnIn2S4/BiPO4preparation method of p-n heterojunction photocatalyst, and preparation method is used for preparing ZnIn2S4/BiPO4A p-n heterojunction photocatalyst.
Further, adding nano spherical bismuth phosphate and indium zinc sulfide into a solvent, and then carrying out hydrothermal reaction to prepare Bi2MoO6/BiPO4A p-n heterojunction photocatalyst.
Further, the method comprises the following steps:
step 1: adding bismuth nitrate and trisodium phosphate into a solvent, and carrying out hydrothermal reaction to prepare nano spherical bismuth phosphate;
step 2: adding zinc acetate, indium nitrate and cysteine into a solvent, and carrying out hydrothermal reaction to prepare indium zinc sulfide;
and step 3: adding the nano spherical bismuth phosphate prepared in the step 1 and the indium zinc sulfide prepared in the step 2 into a solvent, and carrying out hydrothermal reaction to prepare ZnIn2S4/BiPO4A p-n heterojunction photocatalyst.
Furthermore, the molar ratio of the bismuth nitrate to the trisodium phosphate in the step 1 is 1-3: 1-3.
Further, the molar ratio of the zinc acetate to the indium nitrate to the cysteine in the step 2 is 1: 1-2: 6-8; the mass ratio of the indium zinc sulfide to the bismuth phosphate in the step 3 is 5-9: 10.
Further, the reaction temperature of the hydrothermal method in the step 1 is 120-170 ℃, and the reaction time is 5-8 hours; the reaction temperature of the hydrothermal method in the step 2 and the step 3 is 120-200 ℃, and the reaction time is 10-28 hours.
Further, the method specifically comprises the following steps:
step 1: adding bismuth nitrate and trisodium phosphate into ethylene glycol, and carrying out hydrothermal reaction to prepare nano spherical bismuth phosphate, wherein the mass ratio of the bismuth nitrate to the trisodium phosphate is 1:1, the reaction temperature is 160 ℃, and the reaction time is 6 hours;
step 2: adding zinc acetate, indium nitrate and cysteine into deionized water, and carrying out hydrothermal reaction to prepare ZnIn2S4The mass ratio of zinc acetate to indium nitrate to cysteine is 1:2:8, the reaction temperature is 180 ℃, and the reaction time is 12 hours;
and step 3: adding 0.07g of ZnIn prepared in step 2 to methanol2S4Adding 0.1g of nano-spherical bismuth phosphate prepared in the step 1 after ultrasonic dispersion, and carrying out hydrothermal reaction to prepare ZnIn2S4/BiPO4The reaction temperature of the p-n heterojunction photocatalyst by a hydrothermal method is 160-200 ℃, and the reaction time is 10-15 h.
ZnIn of the invention2S4/BiPO4p-n heterojunction photocatalyst or ZnIn of the invention2S4/BiPO4ZnIn obtained by preparation method of p-n heterojunction photocatalyst2S4/BiPO4The application of the p-n heterojunction photocatalyst in degrading nitrate in water has the nitrate degradation rate of 82.2%.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention prepares ZnIn by a hydrothermal method2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst is simple to operateThe method is economical and environment-friendly, and templates such as surfactants and the like are not required to be added in the preparation process. And, ZnIn2S4/BiPO4The p-n heterojunction photocatalyst exhibits a specific ZnIn ratio2S4And BiPO4The p-n obviously improves the photocatalytic activity, the specific surface area and the pore volume of the material are obviously improved, and the large specific surface area is favorable for adsorbing more nitrate ions during photocatalysis and is favorable for improving the photocatalytic activity of the heterojunction photocatalyst.
Drawings
FIG. 1 shows BiPO of different shapes in the examples4SEM image of particles, wherein a represents BiPO having a shape of nanosphere in example 14Particles; b represents BiPO having an irregular shape in example 34(ii) a c represents the octahedral BiPO in example 24(ii) a d represents BiPO of example 4 in the form of a cubic body4Particles;
FIG. 2 is ZnIn2S4SEM picture of (1);
FIG. 3 is ZnIn in example 12S4/BiPO4p-n heterojunction photocatalyst (ZnIn)2S4And BiPO4In a mass ratio of 7: 10);
FIG. 4 is ZnIn in example 52S4/BiPO4p-n heterojunction photocatalyst (ZnIn)2S4And BiPO4In a mass ratio of 1: 2);
FIG. 5 is ZnIn in example 62S4/BiPO4p-n heterojunction photocatalyst (ZnIn)2S4And BiPO4In a mass ratio of 9: 10).
Detailed Description
Heterojunction, an interface region formed by two different semiconductors contacting each other. The heterojunctions can be classified into homotype heterojunctions (P-P junctions or N-N junctions) and heterotype heterojunctions (P-N or P-N) according to the conductivity type of the two materials, and the multilayer heterojunctions are called heterostructures. The conditions under which the heterojunction is typically formed are: both semiconductors have similar crystal structures, close atomic spacings, and thermal expansion coefficients. Heterojunctions can be fabricated using techniques such as interfacial alloying, epitaxial growth, vacuum deposition, and the like.
The invention prepares ZnIn by a hydrothermal method2S4/BiPO4p-n heterojunction photocatalyst, ZnIn2S4/BiPO4The p-n heterojunction photocatalyst is of type II, which means that the energy band structures of the two materials belong to a type II staggered mode. The preparation method is simple to operate, economical and environment-friendly, and templates such as surfactants and the like are not required to be added in the preparation process. Under the induction of sunlight, ZnIn is used2S4/BiPO4The p-n type heterojunction composite photocatalyst removes nitrate radicals in water, has strong catalytic performance, has removal efficiency of the nitrate radicals in underground water up to 85 percent, and can meet the requirement of national drinking water quality standard. The hydrothermal process of the present invention includes conventional hydrothermal process operations.
The preparation method comprises the following steps:
step 1: adding bismuth nitrate and trisodium phosphate into ethylene glycol, and carrying out hydrothermal reaction to prepare nano spherical bismuth phosphate, wherein the mass ratio of bismuth nitrate to trisodium phosphate is 10-13: 10, the hydrothermal reaction temperature is 120-170 ℃, and the reaction time is 5-8 h;
step 2: adding zinc acetate, indium nitrate and cysteine into deionized water, and carrying out hydrothermal reaction to prepare indium zinc sulfide, wherein the molar ratio of zinc acetate, indium nitrate and cysteine is 1: 1-2: 6-8; the reaction temperature of the hydrothermal method is 120-200 ℃, and the reaction time is 10-16 h;
and step 3: adding the indium zinc sulfide prepared in the step 2 and the bismuth phosphate prepared in the step 1 into deionized water, and carrying out hydrothermal reaction to prepare ZnIn2S4/BiPO4The mass ratio of indium zinc sulfide to bismuth phosphate of the p-n heterojunction photocatalyst is 5-9: 10, the reaction temperature of a hydrothermal method is 160-200 ℃, and the reaction time is 10-15 hours.
The reagents used in the present invention are shown in Table 1, and the equipment used is shown in Table 2. The drug was not further purified before use, and the water used in the experiment was deionized water.
TABLE 1 reagent information
TABLE 2 Instrument information
The sample morphology and size of the present invention were characterized by Scanning Electron Microscopy (SEM).
In order to make the objects and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings 1 to 5 and examples and comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Therefore, within the scope of the claims and their equivalents, the invention may be practiced otherwise than as specifically described below.
Example 1:
according to the technical scheme, the embodiment provides the ZnIn2S4/BiPO4 heterojunction photocatalyst, the preparation method and the application thereof. The method comprises the following steps:
step 1: 1.455g of Bi (NO)3)3·5H2O and 1.14g Na3PO4·12H2O dissolved in 100mL of C2H6O2Then stirring for 5-8 h at room temperature to obtain a precipitate, washing the precipitate with ethanol for three times at a speed of 11000rpm, and then adding 60ml of 2mol/L phosphoric acid aqueous solution into the precipitate to form a mixed solution. Subsequently, the mixed solution was transferred to a 100ml stainless steel autoclave lined with polytetrafluoroethylene, and then heated to 160 ℃ for 6 hours. Centrifuging to collect precipitate, washing with ethanol for three times, drying at 60 deg.C for 24 hr, and grinding into powder to obtain nanometer spherical BiPO composed of thin sheets4SEM picture as shown in figure 1, nano-spherical BiPO4The particle size of the (B) is 500 to 800 nm.
Step 2: adding 0.378mmol of Zn (CH)3COO)2·2H2O、0.756mmol In(NO3)3·6H2O and 3mmol C3H7NO2S is added into 20mL of deionized water, the molar ratio is 1:2:8, and cysteine plays a role in reducing the agglomeration of materials; carrying out effective adsorption on pollutants), stirring at room temperature for 1-4 h, transferring the mixed solution into a 100mL lined kettle, heating to 180 ℃ in an oven, keeping for 12h, cooling, washing the synthesized product with deionized water and ethanol alternately for three times, drying the sample in a vacuum drying oven at 70 ℃ for 24h, and grinding to obtain the indium zinc sulfide. As shown in FIG. 2, ZnIn2S4Is in the shape of a micron sphere consisting of countless nano-flakes, and the particle size is 2-3 mu m.
And step 3: BiPO prepared in the step 14And indium zinc sulfide (ZnIn) prepared in step 22S4) Adding into deionized water, wherein BiPO4And ZnIn2S4The mass ratio of the mixed liquid to the mixed liquid is 7:10, and the mixed liquid is transferred to a polytetrafluoroethylene lining reaction kettle after being subjected to ultrasonic treatment for 30 min. Then, the mixture is put into an oven and heated to 180 ℃ for 12 h. After the oven is cooled to room temperature, ZnIn is obtained2S4/BiPO4A heterojunction photocatalyst.
Mixing heterojunction photocatalyst and underground water (nitrate concentration is 50mg/L) at a mass ratio of 1:10, stirring for 30min under the condition of no light (dark reaction) to reach adsorption balance, opening a condensate pipe in a photochemical protection box after the dark reaction is finished to keep the temperature in the photoreaction box constant, then turning on a light source (300W, xenon lamp) and continuously stirring by magnetic force, centrifuging, taking supernatant (4mL) once every 10min by using a pipette, irradiating for 60min by using 300W xenon lamp light totally, measuring the concentration C of the supernatant at 356nm by using an ultraviolet spectrophotometer, and using C/C for the photocatalytic performance of the catalyst0Evaluation of wherein C0Is the concentration of the nitrate radical solution before photocatalytic degradation. The degradation rate of nitrate was recorded in table 1.
ZnIn was performed using a conventional BET tester2S4、BiPO4And ZnIn2S4/BiPO4The performance test of p-n shows that: ZnIn2S4、BiPO4Respectively has a specific surface area of 100.0427m2·g-1And 5.3011m2·g-1The pore volumes are respectively 0.206cm3·g-1And 0.022cm3·g-1，ZnIn2S4/BiPO4p-n (ZnIn2S4And BiPO4Has a mass ratio of 7:10) is 87.3458m2·g-1The pore volume is 0.223cm3·g-1。BiPO4The pure sample has the smallest specific surface area, ZnIn2S4The specific surface area of the pure sample is the largest with ZnIn2S4Increase in content of ZnIn2S4/BiPO4The specific surface area of the p-n composite material is gradually increased, and more uniform nanoflowers are gradually formed at the same time, namely ZnIn2S4When the content reaches 70%, the specific surface area and the pore volume of the photocatalyst reach the maximum value of the composite material, and the appearance of the sample is the best.
Example 2:
ZnIn of the present example2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst was the same as in example 1, except that BiPO prepared in the preparation method was used4In different shapes, BiPO in the present embodiment4Is octahedral and is prepared by the following steps:
adding nitric acid into 40ml deionized water, adjusting pH value to 1, and respectively weighing 2mmol of Bi (NO)3)3·5H2O and 2mmol Na3PO4·12H2And O, dissolving in the solution, stirring at room temperature until the solution is completely dissolved, and performing ultrasonic treatment for 30 min. And then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, preserving the heat at 190 ℃ for 24 hours, and naturally cooling to room temperature. Centrifuging the product, washing with deionized water and anhydrous ethanol several times, vacuum drying at 60 deg.C for 18h, grinding into powder, and collecting octahedron BiPO4And (3) sampling. As shown in FIG. 1c, the sample showed an octahedral shape with a height of about 4 μm and a length of about 3 μm, surface defects, and uneven particle size, but the overall structure was regular and the agglomeration effect was not significant.
The remaining conditions were unchanged and the nitrate degradation rate was recorded in table 1.
Example 3:
ZnIn of the present example2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst was the same as in example 1, except that BiPO prepared in the preparation method was used4In different shapes, BiPO in the present embodiment4The preparation method is the same as that of example 2, except that nitric acid is not added to adjust the pH during the preparation process. As shown in FIG. 1b, the sample particles are very disordered and aggregated, and are irregular in morphology, the agglomeration effect is obvious, and the average particle size of the particles is about 100-200 nm.
The remaining conditions were unchanged and the nitrate degradation rate was recorded in table 1.
Example 4:
ZnIn of the present example2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst is the same as that of example 1, except that BiPO is used in the preparation method4In the present embodiment, BiPO is used4Is in the shape of a cube. The preparation method of the cubic BiPO4 is the same as that in example 2, except that no nitric acid is added to adjust the pH during the preparation process, and 10g of mannitol is added to deionized water and added to the reaction system. As shown in FIG. 1d, the sample was cubic, with a side length of about 1 μm, surface defects, and particles of non-uniform size, but the whole was more regular.
The remaining conditions were unchanged and the nitrate degradation rate was recorded in table 1.
From the data of examples 1 to 4 and table 1, it can be found that smaller particle size can provide more surface atoms and larger area, so that the catalyst has higher catalytic activity. Nanospheres should exhibit better photocatalytic properties compared to irregular, cubic, octahedral particles. BiPO4When the shape of the photocatalyst is nano-spherical, the efficiency of removing nitrate radicals in underground water by the heterojunction photocatalyst is high and reaches 82.2%.
Example 5
ZnIn of the present example2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst is the same as that of the example 1, and the difference is only that ZnIn is prepared in the preparation process2S4And BiPO4Of p-nZnIn of this example was added in different amounts2S4/BiPO4ZnIn in p-n heterojunction photocatalyst2S4And BiPO4The mass ratio of (A) to (B) was 1:2, and the degradation rate of nitrate was recorded in Table 1, while the other conditions were unchanged.
Example 6
ZnIn of the present example2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst is the same as that of the example 1, and the difference is only that ZnIn is prepared in the preparation process2S4And BiPO4The amount of p-n added was varied, ZnIn of this example2S4/BiPO4ZnIn in p-n heterojunction photocatalyst2S4And BiPO4The mass ratio of (A) to (B) was 9:10, the remaining conditions were unchanged, and the degradation rate of nitrate was recorded in Table 1.
From the data in Table 1, it can be seen that ZnIn2S4/BiPO4ZnIn in p-n heterojunction photocatalyst2S4And BiPO4When the mass ratio of (1) to (2) is 7:10, as shown in fig. 3, the composite material presents uniform micro-flowers and is attached with a few nano-rods, and the degradation rate of the composite material to nitrate in groundwater is the highest and reaches 82.2%. As shown in FIG. 4, when ZnIn2S4/BiPO4ZnIn in heterojunction photocatalyst2S4And BiPO4When the mass ratio of (1: 2) is 1, the shape of the popcorn composed of the nanosheets appears, but the existence of the nanoparticles is not seen, and nanorods slightly ranging from 100 to 200nm in width are attached to the surface of the popcorn. As shown in FIG. 5, when ZnIn2S4/BiPO4ZnIn in heterojunction photocatalyst2S4And BiPO4The mass ratio of (2) to (3) is 9:10, the material takes on a relatively irregular shape of the micro-flowers, and the material attached to the surface of the micro-flowers is irregular.
When ZnIn is present2S4/BiPO4With BiPO in a heterojunction photocatalyst4At a mass ratio of 7:10, ZnIn2S4/BiPO4The degradation rate of the heterojunction photocatalyst to nitrate in the underground water reaches 82.2%, and meanwhile, only the nano-spherical BiPO is adopted4As photocatalyst for reducing nitrate radicalThe degradation rate is only 15.9%, and in addition, only ZnIn is adopted2S4When the photocatalyst is used for degrading nitrate radical, the degradation rate is only 23.4 percent, and ZnIn can be seen2S4/BiPO4The catalytic activity of the heterojunction photocatalyst is improved and is shown to be higher than that of ZnIn alone2S4And BiPO4The material has high photocatalytic activity, the specific surface area and the pore volume are obviously improved, and the large specific surface area is favorable for adsorbing more nitrate ions during photocatalysis and is favorable for improving the photocatalytic activity of the heterojunction photocatalyst.
Comparative example 1
The preparation method of the photocatalyst in this example is the same as that in example 1, except that the target of the catalyst action is different, the target in this example is sulfate, sodium sulfate can be selected, the other conditions are not changed, and the degradation rate of the sulfate is recorded in table 1.
Comparative example 2
The photocatalyst preparation method of this example was the same as that of example 1, except that the target of the catalyst action was different, and the target in this example was fluoride, and fluoride was optionally used, and the other conditions were not changed, and the degradation rate of fluoride was recorded in table 1.
The data of comparative examples 1-2 and table 1 show that the heterojunction photocatalyst has high removal efficiency on nitrate in underground water and low removal efficiency on sulfate and fluoride, so that the heterojunction photocatalyst has a specific recognition effect on removal of nitrate and has a good application prospect.
TABLE 1 Effect of different conditions on the degradation rate of nitrate in groundwater
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that the present invention can be practiced without departing from the spirit and scope of the appended claims.
Claims (3)
1. ZnIn2S4/BiPO4The preparation method of the p-n heterojunction photocatalyst is characterized by comprising the following steps:
step 1: adding bismuth nitrate and trisodium phosphate into a solvent, and carrying out hydrothermal reaction to prepare nano spherical bismuth phosphate;
step 2: adding zinc acetate, indium nitrate and cysteine into a solvent, and carrying out hydrothermal reaction to prepare indium zinc sulfide;
and step 3: adding the nano spherical bismuth phosphate prepared in the step 1 and the indium zinc sulfide prepared in the step 2 into a solvent, and carrying out hydrothermal reaction to prepare ZnIn2S4/BiPO4A p-n heterojunction photocatalyst;
the molar ratio of the bismuth nitrate to the trisodium phosphate in the step 1 is 1-3: 1-3;
the molar ratio of the zinc acetate to the indium nitrate to the cysteine in the step 2 is 1: 1-2: 6-8; the mass ratio of the indium zinc sulfide to the bismuth phosphate in the step 3 is 5-9: 10;
the reaction temperature of the hydrothermal method in the step 1 is 120-170 ℃, and the reaction time is 5-8 h; the reaction temperature of the hydrothermal method in the step 2 and the step 3 is 120-200 ℃, and the reaction time is 10-28 hours;
the ZnIn2S4/BiPO4The specific surface area of the p-n heterojunction photocatalyst is 87.3458m2× g-1Pore volume of 0.223cm3× g-1；
The ZnIn2S4/BiPO4The preparation raw materials of the p-n heterojunction photocatalyst are nano spherical bismuth phosphate and indium zinc sulfide, the particle size of the nano spherical bismuth phosphate is 80-150 nm, and the specific surface area of the nano spherical bismuth phosphate is 5.3011m2× g-1Pore volume of 0.022cm3×g-1；
The specific surface area of the indium zinc sulfide is 100.0427m2× g-1Pore volume of 0.206 cm3× g-1。
2. The ZnIn of claim 12S4/BiPO4The preparation method of the p-n heterojunction photocatalyst is characterized by specifically comprising the following steps:
step 1: adding bismuth nitrate and trisodium phosphate into ethylene glycol, and carrying out hydrothermal reaction to prepare nano spherical bismuth phosphate, wherein the mass ratio of the bismuth nitrate to the trisodium phosphate is 1:1, the reaction temperature is 160 ℃, and the reaction time is 6 hours;
step 2: adding zinc acetate, indium nitrate and cysteine into deionized water, and carrying out hydrothermal reaction to prepare ZnIn2S4The mass ratio of zinc acetate to indium nitrate to cysteine is 1:2:8, the reaction temperature is 180 ℃, and the reaction time is 12 hours;
and step 3: adding 0.07g of ZnIn prepared in step 2 to methanol2S4Adding 0.1g of nano-spherical bismuth phosphate prepared in the step 1 after ultrasonic dispersion, and carrying out hydrothermal reaction to prepare ZnIn2S4/BiPO4The reaction temperature of the p-n heterojunction photocatalyst by a hydrothermal method is 160-200 ℃, and the reaction time is 10-15 h.
3. The ZnIn of claim 22S4/BiPO4ZnIn obtained by preparation method of p-n heterojunction photocatalyst2S4/BiPO4The application of the p-n heterojunction photocatalyst in degrading nitrate in water has the nitrate degradation rate of 82.2%.
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