CN108187701B - Preparation method of AgCl/BiOCl photocatalyst with tubular AgCl structure - Google Patents
Preparation method of AgCl/BiOCl photocatalyst with tubular AgCl structure Download PDFInfo
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- CN108187701B CN108187701B CN201810088535.7A CN201810088535A CN108187701B CN 108187701 B CN108187701 B CN 108187701B CN 201810088535 A CN201810088535 A CN 201810088535A CN 108187701 B CN108187701 B CN 108187701B
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 123
- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 111
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 5
- 239000011565 manganese chloride Substances 0.000 claims abstract description 5
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 229940099607 manganese chloride Drugs 0.000 abstract description 3
- 235000002867 manganese chloride Nutrition 0.000 abstract description 3
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 15
- 229940012189 methyl orange Drugs 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000002071 nanotube Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/08—Halides
- B01J27/10—Chlorides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/027—Compounds of F, Cl, Br, I
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
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Abstract
The invention belongs to the technical field of photocatalyst preparation, and relates to a preparation method of an AgCl/BiOCl photocatalyst with a tubular AgCl structure, wherein a hydrothermal method is adopted to prepare a novel AgCl/BiOCl photocatalyst loaded with a nano-tubular AgCl structure for the first time, in the specific preparation method, bismuth oxide, hydrochloric acid, silver nitrate and ethanol are used as raw materials, a precursor BiOCl is prepared firstly, a chlorine source (manganese chloride, ferric chloride and the like) and a silver source are added, and the hydrothermal method is adopted to prepare the AgCl-BiOCl composite photocatalyst with a novel structure; the reinforcing phase AgCl in the prepared AgCl/BiOCl photocatalyst is of a tubular shape structure, and the tubular AgCl is tightly connected with a substrate BiOCl lamina; the preparation method is scientific, the preparation process is simple, the preparation cost is low, and the prepared product has a unique structure, excellent performance and good application prospect.
Description
The technical field is as follows:
the invention belongs to the technical field of photocatalyst preparation, and relates to a preparation method of an AgCl/BiOCl photocatalyst with a novel morphology.
Background art:
photocatalysis is one of the hottest technologies in the field of environmental management at present, and has an excellent effect on environmental pollution management. Compared with other pollution treatment technologies, the semiconductor photocatalysis technology has the advantages of multiple types of degradable organic pollutants, high degradation rate, stable property and the like, and is more energy-saving and environment-friendly because sunlight is used as a light source. Conventional photocatalyst TiO2And the ZnO forbidden band is wide, but has no visible light response capability, so that the practical application of the ZnO forbidden band is limited. Currently, there are two main areas of research focus on photocatalysts: first, for conventional TiO2The photocatalyst is modified, such as ion doping, noble metal loading, semiconductor compounding, surface modification and the like; secondly, a novel semiconductor photocatalyst which can respond to visible light and degrade pollutants more efficiently and in an energy-saving manner is explored.
Among a plurality of novel semiconductor photocatalysts, the Bi-O-Cl photocatalyst has better photocatalytic performance, and can promote the separation of photon-generated carriers and reduce the recombination probability due to the unique layered structure and electronic structure, thereby becoming one of research hotspots. However, the absorption in the visible light range of the Bi-O-Cl photocatalyst is not high, and therefore it needs to be modified. In the prior art, ion doping methods, precious metal modification methods, composite heterojunction methods and the like are commonly used in a modification method of a bismuth oxyhalide photocatalytic material, for example, a Pt/BiOCl nanosheet is prepared by researching a subject group of Yuanchong forest in 2013, and the bismuth oxyhalide photocatalytic material has visible light absorption capacity; an AgCl/BiOCl composite photocatalyst modified by AgCl particles is prepared by the research of Liupeng subject group in 2016, and the absorption of the photocatalyst in a visible light range is improved; a2016 recordance university patent ZL2015106941060 discloses a visible light catalyst Ag-AgCl-BiOCl and a preparation method and application thereof, wherein a composite light catalyst Ag-AgCl-BiOCl is obtained by an AgCl and BiOCl coprecipitation method, crystals in the Ag-AgCl-BiOCl consist of BiOCl, AgCl and simple substance Ag, the Ag-AgCl exists in a BiOCl crystal lattice, and the overall appearance is a dispersing agent and a flaky dispersed particle structure. Based on the research, the AgCl/BiOCl photocatalyst with a novel morphology is researched and prepared for the first time (relevant reports never appear in the prior art at present), namely the AgCl/BiOCl composite photocatalyst modified by AgCl nanotubes has strong photoresponse capability and photocatalytic activity.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and seek to design a method for preparing an AgCl/BiOCl photocatalyst with a special structure, in particular to a method for preparing an AgCl/BiOCl photocatalyst with a tubular AgCl structure (hereinafter referred to as AgCl/BiOCl photocatalyst).
In order to achieve the purpose, the preparation method of the AgCl/BiOCl photocatalyst researched and designed by the invention comprises the following steps:
(1) preparation of BiOCl
① adding Bi 0.01-0.05mol2O3Dropwise adding 5-30mL of hydrochloric acid, uniformly stirring until the two mixtures are completely dissolved to form a transparent solution, and dropwise adding ammonia water into the transparent solution to adjust the pH value to 5-10 so that white precipitates appear in the transparent solution to form a suspension;
placing the suspension at the temperature of 30-60 ℃ and continuously magnetically stirring for 20-60 minutes to form white colloid, centrifugally washing the white colloid for three times by using deionized water and absolute ethyl alcohol, drying the white colloid for 24 hours at the temperature of 40-80 ℃, and collecting the white powder of BiOCl;
(2) preparation of AgCl/BiOCl
① weighing 1.0-5.0g AgNO with electronic balance3Placing the powder in an empty beaker, dropwise adding 50-150ml of absolute ethyl alcohol into the beaker, then adding a stirrer, placing the mixture on a magnetic stirrer, and stirring for 10-60min to form a solution A;
② weighing 20-100mg MnCl2Or FeCl3Placing in an empty beaker, dropwise adding 50-150ml of absolute ethyl alcohol into the beaker, then adding a stirrer, and stirring for 10-60min on a magnetic stirrer to form a solution B;
thirdly, weighing 2-8g of BiOCl white powder prepared in the step (1), placing the BiOCl white powder into an empty beaker, dropwise adding 50-150ml of absolute ethyl alcohol into the beaker, placing the beaker into an ultrasonic instrument, carrying out ultrasonic treatment for 10-60min, then adding a stirrer, and stirring the mixture on a magnetic stirrer for 10-60min to form a solution C;
transferring A, B and C into a hydrothermal kettle by a transfer pipette according to the molar ratio of AgCl to BiOCl being 2%, 5% or 10%, placing the hydrothermal kettle into an oven, adjusting the temperature of the oven to raise the temperature of the hydrothermal kettle along with the oven to 120-200 ℃, and then controlling the temperature to 120-200 ℃ and heating for 12-20h to obtain a product solution;
taking out the hydrothermal kettle after heating, cooling the product solution to room temperature in a furnace cooling or water cooling mode, and then carrying out centrifugal treatment on the product solution for 5-8 minutes by using a centrifugal tube at a controlled rotation speed of 8000-; washing the product solution after the centrifugal treatment with deionized water and ethanol for three times respectively;
sixthly, placing the washed product solution in a culture dish, controlling the temperature to be 30-80 ℃ and drying in a drying oven for 24 hours to obtain AgCl/BiOCl photocatalyst powder loaded with AgCl with a nano tubular structure in different proportions (2%, 5% or 10%).
The reinforcing phase AgCl in the AgCl/BiOCl photocatalyst with the tubular AgCl structure prepared by the invention is in a tubular shape structure, the diameter of the tube is 4-6nm, the wall thickness of the tube is 1.5 +/-0.5 nm, and the tube is tightly connected with a substrate BiOCl lamina; the photocatalyst with the structure has larger specific surface area, and is more beneficial to transferring photo-generated electrons and holes to the surface, thereby greatly improving the photocatalytic efficiency.
2% of AgCl, 5% of AgCl or 10% of AgCl is loaded in the AgCl/BiOCl photocatalyst prepared by the method respectively, wherein the loading proportion of 2%, 5% or 10% refers to the molar ratio of AgCl to BiOCl in the AgCl/BiOCl photocatalyst; the performance of degrading pollutant methyl orange under visible light by the AgCl/BiOCl photocatalyst loaded with 5% of AgCl is the best, and for a methyl orange solution with the mass concentration of 80mg/L, the degradation rate of the methyl orange can reach 91% after 60 minutes under visible light.
Compared with the prior art, the novel AgCl/BiOCl photocatalyst loaded with the nanotube AgCl structure is prepared for the first time by a hydrothermal method, and AgCl nanotubes are tightly combined with BiOCl sheets; the catalyst has stronger photoresponse capability and photocatalytic activity, and has good degradation performance on pollutant methyl orange; the preparation method comprises the steps of taking bismuth oxide, hydrochloric acid, silver nitrate and ethanol as raw materials, firstly preparing a precursor BiOCl, then adding a chlorine source (manganese chloride, ferric chloride and the like) and a silver source, and preparing the AgCl-BiOCl composite photocatalyst with a novel structure by a hydrothermal method; the preparation method is scientific, the preparation process is simple, the preparation cost is low, and the prepared product has a unique structure, excellent performance and good application prospect.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of an AgCl/BiOCl photocatalyst according to the present invention.
FIG. 2 is a morphology image of an AgCl/BiOCl photocatalyst related to the invention under a Transmission Electron Microscope (TEM).
FIG. 3 is a selected area electron diffraction pattern (SAED pattern) of AgCl nanotubes in an AgCl/BiOCl photocatalyst according to the present invention.
FIG. 4 is an energy spectrum (EDS diagram) of an AgCl/BiOCl photocatalyst according to the present invention.
FIG. 5 is a high power transmission electron micrograph (TEM image) of AgCl nanotubes in an AgCl/BiOCl photocatalyst according to the present invention.
FIG. 6 is a UV-VIS Diffuse Reflectance Spectrum (DRS) of an AgCl/BiOCl photocatalyst according to the present invention.
FIG. 7 is a schematic diagram of the degradation curve of AgCl/BiOCl photocatalyst loaded with AgCl in different proportions under visible light to methyl orange according to the invention.
The specific implementation mode is as follows:
the invention is further described by way of example with reference to the accompanying drawings.
Example 1:
the preparation method of the AgCl/BiOCl photocatalyst with the tubular AgCl structure comprises the following steps:
(1) preparation of BiOCl
① adding 0.01-0.05mol of bismuth oxide (Bi)2O3) Dripping 5-30mL of hydrochloric acid (HCl), stirring to dissolve the two mixtures completely to form a transparent solution, and dripping ammonia water into the transparent solution(NH3·H2O) to adjust the pH value to 5-10, so that white precipitate appears in the transparent solution to form a suspension;
② the suspension is magnetically stirred at 30-60 deg.C for 20-60 min to form white colloid, and the white colloid is obtained by mixing deionized water and anhydrous ethanol (C)2H5OH) centrifugally washing the white colloid for three times, drying the white colloid for 24 hours at the temperature of 40-80 ℃, and collecting to obtain BiOCl white powder;
(2) preparation of AgCl/BiOCl
① weighing 1.0-5.0g silver nitrate (AgNO) with electronic balance3) Placing the powder in an empty beaker, and adding 50-150ml of anhydrous ethanol (C) dropwise into the beaker2H5OH), then adding a stirrer, and stirring for 10-60min on a magnetic stirrer to form a solution A;
② weighing 20-100mg manganese chloride (MnCl)2) Or ferric chloride (FeCl)3) Placing in an empty beaker, and dropwise adding 50-150ml of anhydrous ethanol (C) into the beaker2H5OH), then adding a stirrer, and stirring for 10-60min on a magnetic stirrer to form a solution B;
③ weighing 2-8g of BiOCl white powder prepared in step (1), placing in an empty beaker, and dropwise adding 50-150ml of absolute ethyl alcohol (C) into the beaker2H5OH), then placing the beaker in an ultrasonic instrument for ultrasonic treatment for 10-60min, then adding a stirrer and stirring on a magnetic stirrer for 10-60min to form a solution C;
transferring A, B and C into a hydrothermal kettle by a transfer pipette according to the molar ratio of AgCl to BiOCl being 2%, 5% or 10%, placing the hydrothermal kettle into an oven, adjusting the temperature of the oven to raise the temperature of the hydrothermal kettle along with the oven to 120-200 ℃, and then controlling the temperature to 120-200 ℃ and heating for 12-20h to obtain a product solution;
taking out the hydrothermal kettle after heating, cooling the product solution to room temperature in a furnace cooling or water cooling mode, and then carrying out centrifugal treatment on the product solution for 5-8 minutes by using a centrifugal tube at a controlled rotation speed of 8000-; washing the product solution after the centrifugal treatment with deionized water and ethanol for three times respectively;
sixthly, placing the washed product solution in a culture dish, controlling the temperature to be 30-80 ℃ and drying in a drying oven for 24 hours to obtain AgCl/BiOCl photocatalyst powder loaded with AgCl with a nano tubular structure in different proportions (2%, 5% or 10%).
The names and molecular formulas of the chemical agents involved in this example are shown in table 1.
TABLE 1
The names and models of the experimental devices in this example are shown in table 2.
TABLE 2
The AgCl/BiOCl photocatalyst prepared in the embodiment has a unique tubular AgCl load structure, and AgCl nanotubes are tightly combined with BiOCl sheets; the diameter of the AgCl nanotube is 4-6nm, and the wall thickness of the tube is 1.5 +/-0.5 nm; the AgCl/BiOCl photocatalyst with the structure has the characteristics of high specific surface area and strong activity, is beneficial to the separation of photo-generated electrons and holes, and can effectively improve the photodegradation rate and the photocatalytic activity.
The phase of the AgCl/BiOCl photocatalyst prepared in this example was found by X-ray powder diffractometer (XRD) testing (specifically as shown in fig. 1), and the 2 θ value of the peak indicated by the arrow in the spectrum corresponded to the standard card of AgCl.
The basic morphology of the AgCl/BiOCl photocatalyst prepared in this example can be known by observing the basic morphology by using a scanning electron microscope (TEM) (as shown in fig. 2), the position with strong contrast is a BiOCl layer sheet, and the part with weak edge contrast is a one-dimensional nanostructure of AgCl; according to the selected region electron diffraction spectrum (shown in figure 3) of the one-dimensional nanostructure of the AgCl/BiOCl photocatalyst, corresponding to AgCl, the phase of the one-dimensional nanostructure can be determined to be AgCl; from the energy spectrum (as shown in fig. 4), the phases of AgCl and BiOCl can be confirmed; the high power transmission electron microscope image (as shown in fig. 5) of the tubular AgCl structure loaded in the AgCl/BiOCl photocatalyst related in this embodiment can clearly see and judge that the "one-dimensional nanostructure" in fig. 2 is a nanotube, thereby determining that the AgCl/BiOCl photocatalyst has a unique structure in which an AgCl nanotube and a lamellar BiOCl are tightly combined together.
Example 2:
in this example, the AgCl/BiOCl photocatalysts loaded with AgCl in different proportions and prepared in example 1 were subjected to a ultraviolet-visible Diffuse Reflection (DRS) test, and the test results are shown in fig. 6: in the range of 360 and 800nm, the light absorption capacity of AgCl/BiOCl loaded with 2% of AgCl, AgCl/BiOCl loaded with 5% of AgCl and AgCl/BiOCl loaded with 10% of AgCl is higher than that of pure BiOCl, so that the AgCl/BiOCl photocatalyst prepared in example 1 has stronger visible light response capacity in the visible light range (390 and 760 nm).
Example 3:
in this example, methyl orange is used as a target pollutant, and a visible light source is applied to perform experimental study on the photodegradability of the prepared AgCl/BiOCl photocatalyst. The AgCl/BiOCl photocatalysts respectively loaded with 2% of AgCl, 5% of AgCl and 10% of AgCl developed in example 1 are proved to have better degradation effect on methyl orange, wherein the AgCl/BiOCl photocatalyst loaded with 5% of AgCl has the best performance of degrading pollutant methyl orange (as shown in figure 7), and for a methyl orange solution with the mass concentration of 80mg/L, the degradation rate of methyl orange can reach 91% after 60 minutes, while the degradation rate of pure BiOCl under the same condition is only 15%.
In this example, Methyl Orange (MO) is used as a degradation product, and the specific degradation experiment is as follows:
preparing an MO aqueous solution with the initial mass concentration of 80mg/L, and then adding an AgCl/BiOCl photocatalyst into the MO aqueous solution with the concentration of 2 mg/mL; photochemical reaction chambers were used to simulate the environment of photocatalytic degradation. Before starting the photocatalytic reaction, the aqueous MO solution was stirred in the dark for 30 minutes to reach the equilibrium of adsorption and desorption; then the MO aqueous solution is exposed to visible light (a xenon lamp is used as a light source, and an optical filter is used for filtering out ultraviolet light to simulate a visible light source), MO is decomposed in a photocatalytic manner under continuous ventilation and stirring, and finally the degradation rate is calculated.
The comparative analysis result is shown in FIG. 7, and the adsorption performance of the AgCl/BiOCl photocatalyst is superior to that of the photocatalyst without AgCl loading. The AgCl/BiOCl photocatalyst loaded with 5% of AgCl has the best adsorption performance, can adsorb 40% when adsorbed in dark for 30min, and can reach a degradation rate of 91% after being illuminated for 60min, while the degradation rate of pure BiOCl is only about 15%, namely the degradation rate of the AgCl/BiOCl photocatalyst loaded with 5% of AgCl is 6 times that of the BiOCl photocatalyst when degraded for 60 min.
In summary, the AgCl/BiOCl photocatalyst prepared in example 1 has excellent photocatalytic activity under visible light. The principle is as follows: firstly, the AgCl/BiOCl photocatalyst has stronger visible light response capability; secondly, the specific surface area of the AgCl/BiOCl photocatalyst material is improved due to the AgCl nanotube-shaped structure, and the adsorption performance of the AgCl/BiOCl photocatalyst material is enhanced, so that the AgCl/BiOCl photocatalyst material can adsorb more pollutant molecules; meanwhile, the loaded AgCl nano-tubular structure increases the active sites of the AgCl/BiOCl photocatalyst material surface reaction, so that the photo-generated carriers can move to the surface more quickly to react, the recombination probability of photo-generated electrons and holes is reduced, and the photocatalytic performance is improved.
Claims (2)
1. A preparation method of an AgCl/BiOCl photocatalyst with a tubular AgCl structure is characterized by comprising the following steps:
(1) preparation of BiOCl
① adding Bi 0.01-0.05mol2O3Dropwise adding 5-30mL of hydrochloric acid, uniformly stirring until the two mixtures are completely dissolved to form a transparent solution, and dropwise adding ammonia water into the transparent solution to adjust the pH value to 5-10 so that white precipitates appear in the transparent solution to form a suspension;
placing the suspension at the temperature of 30-60 ℃ and continuously magnetically stirring for 20-60 minutes to form white colloid, centrifugally washing the white colloid for three times by using deionized water and absolute ethyl alcohol, drying the white colloid for 24 hours at the temperature of 40-80 ℃, and collecting the white powder of BiOCl;
(2) preparation of AgCl/BiOCl
① weighing 1.0-5.0g AgNO with electronic balance3Placing the powder in an empty beaker, dropwise adding 50-150ml of absolute ethyl alcohol into the beaker, then adding a stirrer, placing the mixture on a magnetic stirrer, and stirring for 10-60min to form a solution A;
② weighing 20-100mg MnCl2Or FeCl3Placing in an empty beaker, dropwise adding 50-150ml of absolute ethyl alcohol into the beaker, then adding a stirrer, and stirring for 10-60min on a magnetic stirrer to form a solution B;
thirdly, weighing 2-8g of BiOCl white powder prepared in the step (1), placing the BiOCl white powder into an empty beaker, dropwise adding 50-150ml of absolute ethyl alcohol into the beaker, placing the beaker into an ultrasonic instrument, carrying out ultrasonic treatment for 10-60min, then adding a stirrer, and stirring the mixture on a magnetic stirrer for 10-60min to form a solution C;
transferring A, B and C into a hydrothermal kettle by a transfer pipette according to the molar ratio of AgCl to BiOCl being 2%, 5% or 10%, placing the hydrothermal kettle into an oven, adjusting the temperature of the oven to raise the temperature of the hydrothermal kettle along with the oven to 120-200 ℃, and then controlling the temperature to 120-200 ℃ and heating for 12-20h to obtain a product solution;
taking out the hydrothermal kettle after heating, cooling the product solution to room temperature in a furnace cooling or water cooling mode, and then carrying out centrifugal treatment on the product solution for 5-8 minutes by using a centrifugal tube at a controlled rotation speed of 8000-; washing the product solution after the centrifugal treatment with deionized water and ethanol for three times respectively;
sixthly, placing the washed product solution in a culture dish, controlling the temperature to be 30-80 ℃ and drying in a drying oven for 24 hours to obtain AgCl/BiOCl photocatalyst powder loaded with 2%, 5% or 10% of AgCl with a nano tubular structure respectively.
2. The method for preparing the AgCl/BiOCl photocatalyst with the tubular AgCl structure according to claim 1, wherein the reinforcing phase AgCl in the prepared AgCl/BiOCl photocatalyst with the tubular AgCl structure is in a tubular shape, the diameter of the tube is 4-6nm, the wall thickness of the tube is 1.5 +/-0.5 nm, and the tubular AgCl is tightly connected with a substrate BiOCl lamina; the loading proportion of tubular AgCl in the AgCl/BiOCl photocatalyst with a tubular AgCl structure is 2%, 5% or 10%, and the loading proportion of 2%, 5% or 10% refers to the molar ratio of AgCl to BiOCl in the AgCl/BiOCl photocatalyst.
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