CN109621990A - A kind of preparation method of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet - Google Patents

A kind of preparation method of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet Download PDF

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CN109621990A
CN109621990A CN201910070709.1A CN201910070709A CN109621990A CN 109621990 A CN109621990 A CN 109621990A CN 201910070709 A CN201910070709 A CN 201910070709A CN 109621990 A CN109621990 A CN 109621990A
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bismuth
solution
nanometer sheet
thin
ultra
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武大鹏
王锐
王晓璐
徐芳
高志永
王红菊
曹锟
刘宁
蒋凯
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Henan Normal University
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Henan Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J35/23
    • B01J35/39
    • B01J35/50
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam

Abstract

The invention discloses a kind of preparation methods of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet, belong to the synthesis technical field of catalysis material.Technical solution of the present invention main points are as follows: five nitric hydrate bismuths and neopelex are dissolved in mannitol solution, it is stirred at room temperature to being completely dissolved; take saturated sodium chloride solution to be slowly added in above-mentioned solution; to continue to stir to get white opacity solution; be transferred to react in hydrothermal reaction kettle by acquired solution the ultra-thin bismuth oxychloride nanometer sheet of product is made; take the ultra-thin bismuth oxychloride three-dimensional manometer piece of gained to be distributed in saturation potassium bromide solution, the compound super rich nanometer sheet of three-dimensional structure bismuth oxychloride/bismuth oxybromide to form composition is exchanged by High temperature ion.Operation of the present invention is simple for process, the three-dimensional structure that there is bismuth oxychloride/bismuth oxybromide composite material of synthesis ultra-thin two-dimension nanometer sheet to be self-assembly of, large specific surface area, stable structure.

Description

A kind of preparation of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet Method
Technical field
The invention belongs to the preparation technical fields of catalysis material, and in particular to use solvent structure three-dimensional structure chlorine Bismuth oxide, and the method that three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet is prepared by ion-exchange.
Background technique
In recent years, environmental pollution and energy shortage are the significant challenges that current mankind faces.Photocatalysis technology can be direct Normal-temperature deep reaction is carried out as optical drive using solar energy, therefore with wide in terms of the depollution of environment and new energy development Development prospect.Using conductor oxidate as catalyst, luminous energy is converted into electric energy and chemical energy is that we provide a kind of ideals Using energy source and environmental pollution improvement method.But main problem present in Study on photocatalyst is photoproduction Electron-hole pair recombination probability height and optical response range are relatively narrow.
Bismuth system catalysis material is issued because having special layer structure and relatively narrow forbidden bandwidth in the irradiation of visible light The separation of raw electrons and holes.Bismuth series photocatalyst mainly includes bismuth oxide at present, BiOX, the oxysalt of bismuth and multiple Mould assembly bismuth catalyst etc..Wherein most representative is BiOX (BiOX, X=F, Cl, Br, I) series compound, because of its tool There are unique, excellent electronics and optical characteristics, and is considered to be at the ideal chose being catalyzed under visible optical drive.For One-component photochemical catalyst is difficult to accomplish not only have wide absorption region but also have suitable redox current potential.To solve this problem, People construct special composite material, such as semiconductor-semiconductor (S-S) hetero-junctions, semiconductor-metal (S- using a variety of methods M) hetero-junctions, semiconductor-carbon (S-C) hetero-junctions and multicomponent hetero-junctions.These Bimaterial in terface coupling parts are to material Pattern and photo-generated carrier tool have a significant impact, and then influence its photocatalytic activity.The formation of hetero-junctions is able to suppress light The invalid compound of carrier is given birth to, to greatly improve the photocatalytic activity of catalyst.Since semiconductor composite has centainly Advantage, thus have many further researchs to BiOX composite photo-catalyst recently.Conjunction in relation to BiOCl/BiOBr composite material At also fewer, especially in the two-dimentional BiOCl/BiOBr photocatalyst applications that will have superthin structure in photocatalysis fixed nitrogen side Face.It is well known that BiOCl greater band gap (3.17-3.54 eV), by BiOCl and has narrow band gap BiOBr semiconductors coupling Afterwards, valence band and conduction band positions are more suitable, to effectively enhance visible absorption, inhibit photo-generate electron-hole compound, improve current-carrying The sub- service life.In addition, two-dimensional ultrathin structure makes catalysis material have more high-specific surface area and more how unsaturated surface atom, and And the atom of surface exposure escapes easily from lattice and generates vacancy, largely influences the physicochemical properties of material.Shen Number a kind of preparation method of porous bismuth oxyiodide nano-photo catalytic please be disclosed for a patent of CN201210082112.7, mainly In order to solve existing bismuth oxyiodide in the technical problem of visible region light degradation property difference, but this method preparation process it is cumbersome and A large amount of organic solvents have been used to be unfavorable for being mass produced, furthermore it is low to be prepared for bismuth oxyiodide specific surface area for this method, not Change the photocatalysis performance of bismuth oxyiodide from the root, room for promotion is limited.The patent of Publication No. CN101724839A provides A kind of method prepare BiOCl film using vapor deposition and chemical oxidization method, film obtained have flower-like structure, but system Standby process need to need special instrument and equipment and high-purity gas do protection gas by complicated processes of physical vapor deposition, cost compared with Height, it is complicated for operation.BiOI thin-film electro is made using SILAR method in the patent of Publication No. CN101857382A Pole has application potential in area of solar cell, but required film, operation need to could be made by being repeated as many times in this method Process is relatively complicated.The patent of Publication No. N102974373 A discloses a kind of heterogeneous visible light of bismuth oxychloride/bismuth oxyiodide The preparation method of catalysis material mainly for providing the material with high catalytic activity and stability, but prepares predecessor chlorine Bismuth oxide time-consuming is tediously long, and the later period reacts with bismuth oxyiodide also to be needed by calcining, and the nanometer sheet of formation is thicker and is unfavorable for electronics- Hole efficiently separates.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometers The preparation method of piece, bismuth oxychloride@bismuth oxybromide made from this method have ultra-thin two-dimension structure.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of three-dimensional structure bismuth oxychloride@bromine oxidation The preparation method of bismuth composite ultra-thin nanometer sheet, it is characterised in that specific steps are as follows: by five nitric hydrate bismuth of 0.4-1.5mmol and 0.6-2mmol neopelex is dissolved in the mannitol solution that 25mL molar concentration is 0.1M, is stirred at room temperature to complete Dissolution, takes 5mL saturated sodium chloride solution to be added in above-mentioned solution, continues to stir to get white opacity solution, by acquired solution It is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, the white precipitate for generating reaction is centrifuged after being cooled to room temperature and is distinguished With deionized water and ethanol washing, it is dried in vacuo then at 60 DEG C and the ultra-thin bismuth oxychloride nanometer sheet of product is made, it then will be obtained by 3g Ultra-thin bismuth oxychloride nanometer sheet is distributed in 150-300mL saturation potassium bromide solution, is dried to obtain three-dimensional afterwards for 24 hours in 90 DEG C of stirrings Structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet.
Further preferably, the preparation method of the three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet, it is special Sign is specific steps are as follows: five nitric hydrate bismuth of 1mmol and 1.2mmol neopelex are dissolved in 25mL molar concentration It is complete to dissolution to be stirred at room temperature in the mannitol solution of 0.1M, take 5mL saturated sodium chloride solution to be added in above-mentioned solution, after It is continuous to stir to get white opacity solution, acquired solution is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, room is cooled to It is centrifuged after temperature and the white precipitate that reaction generates is used into deionized water and ethanol washing respectively, be made ultra-thin then at 60 DEG C of vacuum drying Then ultra-thin bismuth oxychloride nanometer sheet obtained by 3g is distributed in 200mL saturation potassium bromide solution, in 90 by bismuth oxychloride nanometer sheet DEG C stirring is dried to obtain three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet afterwards for 24 hours.
Operation of the present invention is simple for process, reproducible, and bismuth oxychloride@bismuth oxybromide obtained is received with ultra-thin two-dimension The three-dimensional structure that rice piece is self-assembly of, large specific surface area, stable structure;Bismuth oxychloride@bismuth oxybromide obtained is compound super rich Nanometer sheet band gap is suitable, is conducive to the separation of photo-generated carrier, while being conducive to that lamella stacking is avoided to cause in catalytic process Performance degradation, thus photocatalysis field with good application prospect.
Detailed description of the invention
Fig. 1 is the SEM figure of ultra-thin bismuth oxychloride nanometer sheet obtained in comparative example 1 of the present invention, picture amplification factor difference It is 50000 times;
Fig. 2 is the SEM figure of the compound super rich nanometer sheet of bismuth oxychloride bismuth oxybromide made from the embodiment of the present invention 1, picture times magnification Number is 50000 times respectively;
Fig. 3 is that ultra-thin bismuth oxychloride nanometer sheet made from comparative example 1 and embodiment 1 of the present invention and bismuth oxychloride@bismuth oxybromide are multiple Close the XRD diagram of super rich nanometer sheet.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment 1
Five nitric hydrate bismuth of 1mmol and 1.2mmol neopelex are dissolved in the sweet dew that 25mL molar concentration is 0.1M In alcoholic solution, it is stirred at room temperature to dissolution completely, takes 5mL saturated sodium chloride solution to be slowly added in above-mentioned solution, continue to stir To white opacity solution, acquired solution is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, is centrifuged after being cooled to room temperature The white precipitate that reaction generates is used into deionized water and ethanol washing respectively, is dried in vacuo then at 60 DEG C and the ultra-thin chlorine oxygen of product is made Change bismuth nanometer sheet;Then ultra-thin bismuth oxychloride nanometer sheet obtained by 3g is distributed in 200mL saturation potassium bromide solution, is stirred in 90 DEG C It mixes to be dried in vacuo afterwards for 24 hours and the compound super rich nanometer sheet BOC/BOB-NS1 of three-dimensional structure bismuth oxychloride bismuth oxybromide is made.
Embodiment 2
Five nitric hydrate bismuth of 1mmol and 1.2mmol neopelex are dissolved in the sweet dew that 25mL molar concentration is 0.1M In alcoholic solution, it is stirred at room temperature to dissolution completely, takes 5mL saturated sodium chloride solution to be slowly added in above-mentioned solution, continue to stir To white opacity solution, acquired solution is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, is centrifuged after being cooled to room temperature The white precipitate that reaction generates is used into deionized water and ethanol washing respectively, is dried in vacuo then at 60 DEG C and the ultra-thin chlorine oxygen of product is made Change bismuth nanometer sheet;Then ultra-thin bismuth oxychloride nanometer sheet obtained by 3g is distributed in 300mL saturation potassium bromide solution, is stirred in 90 DEG C It mixes to be dried in vacuo afterwards for 24 hours and the compound super rich nanometer sheet BOC/BOB-NS2 of three-dimensional structure bismuth oxychloride bismuth oxybromide is made.
Comparative example 1
Five nitric hydrate bismuth of 1mmol and 1.2mmol neopelex are dissolved in the sweet dew that 25mL molar concentration is 0.1M In alcoholic solution in solution, it is stirred at room temperature to dissolution completely, 5mL saturated sodium chloride solution is taken to be slowly added in above-mentioned solution, continue White opacity solution is stirred to get, acquired solution is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, is cooled to room temperature It is centrifuged afterwards and the white precipitate that reaction generates is used into deionized water and ethanol washing respectively, it is super that obtained product is dried in vacuo then at 60 DEG C Thin bismuth oxychloride three-dimensional manometer piece BOC.
In conclusion preparation process of the present invention is relatively more simple, condition is easily controllable.In addition, gained bismuth oxychloride@bromine The three-dimensional structure that there is bismuth oxide composite material ultra-thin two-dimension nanometer sheet to be self-assembly of, specific surface area with higher are enriched Active site;Meanwhile composite construction is conducive to the generation and separation of photo-generate electron-hole pair, three-dimensional structure has in catalysis Conducive to the stacking for avoiding piece interlayer, the stability of catalyst is improved.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of preparation method of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet, it is characterised in that specific step Suddenly are as follows: five nitric hydrate bismuth of 0.4-1.5mmol and 0.6-2mmol neopelex, which are dissolved in 25mL molar concentration, is It in the mannitol solution of 0.1M, is stirred at room temperature to being completely dissolved, 5mL saturated sodium chloride solution is taken to be added in above-mentioned solution, after It is continuous to stir to get white opacity solution, acquired solution is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, room is cooled to It is centrifuged after temperature and the white precipitate that reaction generates is used into deionized water and ethanol washing respectively, be dried in vacuo then at 60 DEG C and product is made Then it is molten to be distributed to 150-300mL saturation potassium bromide by ultra-thin bismuth oxychloride nanometer sheet for ultra-thin bismuth oxychloride nanometer sheet obtained by 3g In liquid, three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet is dried to obtain afterwards for 24 hours in 90 DEG C of stirrings.
2. the preparation method of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet according to claim 1, Be characterized in that specific steps are as follows: by five nitric hydrate bismuth of 1mmol and 1.2mmol neopelex be dissolved in 25mL moles it is dense Degree is to be stirred at room temperature to dissolution completely in the mannitol solution of 0.1M, 5mL saturated sodium chloride solution is taken to be added in above-mentioned solution, Continue to stir to get white opacity solution, acquired solution is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 3h, is cooled to It is centrifuged after room temperature and the white precipitate that reaction generates is used into deionized water and ethanol washing respectively, be made super then at 60 DEG C of vacuum drying Then ultra-thin bismuth oxychloride nanometer sheet obtained by 3g is distributed in 200mL saturation potassium bromide solution by thin bismuth oxychloride nanometer sheet, in 90 DEG C of stirrings are dried to obtain three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet afterwards for 24 hours.
CN201910070709.1A 2018-06-14 2019-01-25 A kind of preparation method of three-dimensional structure bismuth oxychloride@bismuth oxybromide composite ultra-thin nanometer sheet Pending CN109621990A (en)

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CN111686783B (en) * 2020-07-27 2022-03-18 齐鲁理工学院 2D/2D heterojunction BiO2-x/g-C3N4 nanosheet composite material for photocatalytic nitrogen reduction
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CN115124076B (en) * 2022-07-07 2023-03-10 中南大学 Method for preparing bismuth-based oxyhalide in batches
CN115646513A (en) * 2022-09-22 2023-01-31 西北大学 Preparation method and application of BiOBr/BiOI/SDBS composite material with microspherical appearance
CN115779936A (en) * 2022-10-26 2023-03-14 江苏科技大学 Spherical BiOBr/BiOCl composite material and preparation method and application thereof
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Application publication date: 20190416