CN107876074A - g‑C3N4The preparation method of nano particle/flower-shaped BiOI composites - Google Patents

g‑C3N4The preparation method of nano particle/flower-shaped BiOI composites Download PDF

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Publication number
CN107876074A
CN107876074A CN201710986163.5A CN201710986163A CN107876074A CN 107876074 A CN107876074 A CN 107876074A CN 201710986163 A CN201710986163 A CN 201710986163A CN 107876074 A CN107876074 A CN 107876074A
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flower
nano particle
bioi
composites
shaped bioi
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CN107876074B (en
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申乾宏
尤增宇
于洋
王辉
陈昊
杨辉
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • B01J27/24Nitrogen compounds
    • B01J35/39
    • 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
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
    • 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
    • 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures

Abstract

The present invention relates to field of semiconductor materials, it is desirable to provide a kind of g C3N4The preparation method of nano particle/flower-shaped BiOI composites.Including:For rich nitrogen precursor powder after Overheating Treatment, grinding obtains powdered g C3N4;It is dispersed in strong acid solution after condensing reflux, wash products are until neutral, acquisition g C3N4Nano particle;By Bi (NO3)3·5H2O and KI is added in the mixed solution of deionized water and ethylene glycol, the laggard water-filling thermal response of stirring and dissolving, is dried after obtained sediment washing, is obtained flower-shaped BiOI;By flower-shaped BiOI and g C3N4Nano particle is scattered in deionized water, is stirred after sonic oscillation;By sediment undergoes washing, drying after centrifugation, final product is obtained.The preparation method kind of the present invention is simple, easy to operate.The g C of uniform load can be prepared3N4Nano particle/flower-shaped BiOI composites, it is possessed high photoproduction carrier separation efficiency, high visible absorbability, be g C3N4The research of based nano composite material provides new thinking.

Description

g-C3N4The preparation method of nano particle/flower-shaped BiOI composites
Technical field
The present invention relates to field of semiconductor materials, more particularly to a kind of g-C3N4Nano particle/flower-shaped BiOI composites Preparation method.
Background technology
In recent years, conductor photocatalysis material is used as a kind of green, Sustainable New material in water pollutant Prepared by processing, hydrogen energy source, huge application prospect is shown in terms of greenhouse gases and organic contamination gas clean-up and is ground Study carefully value, thus it is of great interest.But there is obvious photo-generated carrier low separation efficiency for single semiconductor Problem, therefore heterojunction semiconductor composite rapidly becomes the focus of this research field.Two kinds of semiconductor composites lead to The transfer of light induced electron and hole between different semiconductor energy gaps is crossed to realize photo-generate electron-hole to efficiently separating.Most Closely, the catalysis material of BiOX (X=Cl, Br, I) series receives extensive research.Wherein BiOI is wide because of its narrower forbidden band Spend (~1.8eV), higher visible absorption ability, while suitable position of energy band, preferable stability and 2D stratiform knots Structure and turn into very promising photochemical catalyst.However, BiOI is there is also the problem of photo-generated carrier low separation efficiency, therefore It is carried out with other semi-conducting materials compound to lift the study hotspot that its photo-generated carrier separative efficiency is the research field.
Class graphitic carbon nitride (g-C3N4) increasingly received significant attention as a kind of new visible light catalytic material. g-C3N4Energy gap be 2.7eV, make it that also there is catalytic activity in visible region.In addition g-C3N4By reserves on the earth most Horn of plenty two kinds of chemical elements C and N composition, nonhazardous and prepare cost it is cheap.Therefore, g-C3N4With its excellent semiconductor Characteristic, high chemical stability, nontoxic easily prepare and the cheap characteristic of cost has bright application prospect in photocatalysis field.Have Researcher carries out both compound g-C to be prepared3N4/ BiOI composites;Also researcher is prepared into by ionic liquid To the spherical BiOI of micron and and g-C assembled by BiOI nanometer sheets3N4Carry out compound, make its photocatalytic degradation methylene blue Ability is improved significantly;Also BiOI micron films have been prepared by hydro-thermal method in researcher, and with block g-C3N4Carry out It is compound, its specific surface area is increased dramatically, it is seen that the performance of photocatalysis degradation organic contaminant is also improved.But It is that the compound of the two still has the problem of compound uneven in microstructure.As can be seen here, it is necessary to g-C3N4/BiOI Composite carries out structural adjustment, further to improve its compound uniformity.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of g-C3N4Nano particle/flower The preparation method of shape BiOI composites.
To solve the above problems, the solution of the present invention is:
A kind of g-C is provided3N4The preparation method of nano particle/flower-shaped BiOI composites, comprises the following steps:
Step A:Using at least one of cyanamide, dicyandiamide or melamine as rich nitrogen presoma, its powder is taken to fall It is placed in after entering corundum crucible boat in vacuum tube furnace;It is passed through protective atmosphere to drain the air in vacuum tube furnace, at overheat Reason obtains block g-C3N4, further grinding, obtains powdered g-C3N4
Step B:The powdered g-C by made from3N4It is dispersed in strong acid solution, g-C3N4Mass ratio with strong acid solution is 1 : 50~1: 200;Strong acid solution is formulated by the concentrated sulfuric acid that mass ratio is 1: 1~1: 3 with concentrated nitric acid, both mass fractions Respectively 98% and 68%;By scattered gained mixed liquor after 2~10h of condensing reflux under the conditions of 60~80 DEG C, deionized water is used Wash products are until neutral, acquisition g-C repeatedly3N4Nano particle;
Step C:By Bi (NO3)3·5H2O and KI add prepared by deionized water and ethylene glycol in mass ratio 1: 1~1: 5 and Into mixed solution in, and make KI mass percent concentration be 1~5%, Bi elements and the mol ratio of I elements is 1: 1;Stirring It is transferred to after dissolving in reactor and carries out hydro-thermal reaction, reaction temperature is 130~180 DEG C, and the reaction time is 12~24h;Will The sediment arrived is subsequently placed in 60 in baking oven first with twice of deionized water centrifuge washing, then with twice of absolute ethyl alcohol centrifuge washing DEG C drying, obtain flower-shaped BiOI;
Step D:By g-C obtained by flower-shaped BiOI and step B3N4Nano particle is scattered in deionized water, g-C3N4With it is flower-shaped BiOI mass ratio is 1: 10~1: 200;After 0.5~2h of sonic oscillation, 12~24h is stirred;By sediment with anhydrous after centrifugation Ethanol cleans three times, is placed in 60 DEG C of drying in baking oven, obtains g-C3N4Nano particle/flower-shaped BiOI composites.
In the present invention, in the step A, heat treatment temperature is 500~600 DEG C, and heat treatment time is 2~10h.
In the present invention, in the step A, the protective atmosphere of tube furnace is argon gas or nitrogen.
The realization principle of the present invention:
The present invention is by preparing flower-shaped BiOI (by thickness in 30~50nm, BiOI nanometer sheet group of the size in micron level Into), the BiOI materials with high surface area are obtained, are g-C of the size in 30nm or so3N4The attachment of nano particle provides bar Part.In addition, surface carries negative electricity, g-C in water using BiOI3N4Nano grain surface positively charged, realize the two electrostatic from group Dress.
Compared with prior art, the beneficial effects of the invention are as follows:
1st, preparation method kind of the invention is simple, easy to operate.
2nd, the g-C of uniform load has been prepared in the present invention3N4Nano particle/flower-shaped BiOI composites, makes it possess height Photo-generated carrier separative efficiency, high visible absorbability, it is g-C3N4The research of based nano composite material provides new think of Road.
Brief description of the drawings
Fig. 1 is g-C3N4The stereoscan photograph (apparent form photo) of nano particle/flower-shaped BiOI composites.
Embodiment
The present invention is described in further detail with reference to embodiment:
g-C3N4The preparation method of nano particle/flower-shaped BiOI composites, comprises the following steps:
Step A:Using at least one of cyanamide, dicyandiamide or melamine as rich nitrogen presoma, its powder is taken to fall It is placed in after entering corundum crucible boat in vacuum tube furnace;It is passed through protective atmosphere to drain the air in vacuum tube furnace, at overheat Reason obtains block g-C3N4, further grinding, obtains powdered g-C3N4
Step B:The powdered g-C by made from3N4It is dispersed in strong acid solution, g-C3N4Mass ratio with strong acid solution is 1 : 50~1: 200;Strong acid solution is formulated by the concentrated sulfuric acid that mass ratio is 1: 1~1: 3 with concentrated nitric acid, both mass fractions Respectively 98% and 68%;By scattered gained mixed liquor after 2~10h of condensing reflux under the conditions of 60~80 DEG C, deionized water is used Wash products are until neutral, acquisition g-C repeatedly3N4Nano particle;
Step C:By Bi (NO3)3·5H2O and KI add prepared by deionized water and ethylene glycol in mass ratio 1: 1~1: 5 and Into mixed solution in, and make KI mass percent concentration be 1~5%, Bi elements and the mol ratio of I elements is 1: 1;Stirring It is transferred to after dissolving in reactor and carries out hydro-thermal reaction, reaction temperature is 130~180 DEG C, and the reaction time is 12~24h;Will The sediment arrived is subsequently placed in 60 in baking oven first with twice of deionized water centrifuge washing, then with twice of absolute ethyl alcohol centrifuge washing DEG C drying, obtain flower-shaped BiOI;
Step D:By g-C obtained by flower-shaped BiOI and step B3N4Nano particle is scattered in deionized water, g-C3N4With it is flower-shaped BiOI mass ratio is 1: 10~1: 200;After 0.5~2h of sonic oscillation, 12~24h is stirred;By sediment with anhydrous after centrifugation Ethanol cleans three times, is placed in 60 DEG C of drying in baking oven, obtains g-C3N4Nano particle/flower-shaped BiOI composites.
The present invention is more fully understood in the professional and technical personnel that the following examples can make this professional, but not with any side The formula limitation present invention.G-C is successfully made by 8 embodiments respectively3N4Nano particle/flower-shaped BiOI composites, each embodiment In test data see the table below 1.
The embodiment tables of data of table 1
Finally, it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention not It is limited to above embodiment, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure Export or all deformations associated are connect, are considered as protection scope of the present invention.

Claims (3)

  1. A kind of 1. g-C3N4The preparation method of nano particle/flower-shaped BiOI composites, it is characterised in that comprise the following steps:
    Step A:Using at least one of cyanamide, dicyandiamide or melamine as rich nitrogen presoma, its powder is taken to pour into just It is placed in after beautiful crucible boat in vacuum tube furnace;It is passed through protective atmosphere to drain the air in vacuum tube furnace, is obtained through Overheating Treatment To block g-C3N4, further grinding, obtains powdered g-C3N4
    Step B:The powdered g-C by made from3N4It is dispersed in strong acid solution, g-C3N4With the mass ratio of strong acid solution for 1: 50~ 1∶200;Strong acid solution is formulated by the concentrated sulfuric acid that mass ratio is 1: 1~1: 3 with concentrated nitric acid, and both mass fractions are respectively 98% and 68%;It is repeatedly clear with deionized water by scattered gained mixed liquor after 2~10h of condensing reflux under the conditions of 60~80 DEG C Product is washed until neutral, acquisition g-C3N4Nano particle;
    Step C:By Bi (NO3)3·5H2O and KI adds what is be formulated by deionized water and ethylene glycol in mass ratio 1: 1~1: 5 In mixed solution, and KI mass percent concentration is set to be 1~5%, Bi elements and the mol ratio of I elements is 1: 1;Stirring and dissolving After be transferred in reactor and carry out hydro-thermal reaction, reaction temperature is 130~180 DEG C, and the reaction time is 12~24h;By what is obtained Sediment is subsequently placed in 60 DEG C of bakings in baking oven first with twice of deionized water centrifuge washing, then with twice of absolute ethyl alcohol centrifuge washing It is dry, obtain flower-shaped BiOI;
    Step D:By g-C obtained by flower-shaped BiOI and step B3N4Nano particle is scattered in deionized water, g-C3N4With flower-shaped BiOI Mass ratio be 1: 10~1: 200;After 0.5~2h of sonic oscillation, 12~24h is stirred;By sediment absolute ethyl alcohol after centrifugation Cleaning three times, 60 DEG C of drying in baking oven are placed in, obtain g-C3N4Nano particle/flower-shaped BiOI composites.
  2. 2. according to the preparation method described in claim 1, it is characterised in that in the step A, heat treatment temperature be 500~ 600 DEG C, heat treatment time is 2~10h.
  3. 3. according to the preparation method described in claim 1, it is characterised in that in the step A, the protective atmosphere of tube furnace is Argon gas or nitrogen.
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CN109395777A (en) * 2018-04-12 2019-03-01 常州大学 A kind of Three-element composite photocatalyst BiOI@UIO-66 (NH2)@g-C3N4Preparation method
CN109847780A (en) * 2019-01-30 2019-06-07 太原理工大学 A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material
CN110075923A (en) * 2019-04-30 2019-08-02 江苏大学 A kind of g-C3N4The bionical construction method and application thereof of/BiOI-pDA@PVDF photocatalysis membrana
CN114160172A (en) * 2021-12-16 2022-03-11 中国船舶重工集团公司第七一九研究所 For CO2Cu/BiOI catalyst for preparing methanol by catalytic hydrogenation and preparation method thereof
CN114522709A (en) * 2022-01-14 2022-05-24 广东工业大学 Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109395777A (en) * 2018-04-12 2019-03-01 常州大学 A kind of Three-element composite photocatalyst BiOI@UIO-66 (NH2)@g-C3N4Preparation method
CN109847780A (en) * 2019-01-30 2019-06-07 太原理工大学 A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material
CN110075923A (en) * 2019-04-30 2019-08-02 江苏大学 A kind of g-C3N4The bionical construction method and application thereof of/BiOI-pDA@PVDF photocatalysis membrana
CN114160172A (en) * 2021-12-16 2022-03-11 中国船舶重工集团公司第七一九研究所 For CO2Cu/BiOI catalyst for preparing methanol by catalytic hydrogenation and preparation method thereof
CN114522709A (en) * 2022-01-14 2022-05-24 广东工业大学 Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof
CN114522709B (en) * 2022-01-14 2023-10-31 广东工业大学 Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof

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