CN106915771A - One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template - Google Patents

One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template Download PDF

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CN106915771A
CN106915771A CN201710107373.2A CN201710107373A CN106915771A CN 106915771 A CN106915771 A CN 106915771A CN 201710107373 A CN201710107373 A CN 201710107373A CN 106915771 A CN106915771 A CN 106915771A
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wire
mesoporous
bismuth
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prepared
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CN106915771B (en
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钱坤
谢吉民
宋佳宁
姜志峰
魏巍
夏莉
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Jiangsu University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00Compounds of bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18Arsenic, antimony or bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides one kind with C3N4The method that mesoporous wire bismuth titanates is prepared for template, step is as follows:(1) weigh a certain amount of bismuth nitrate in beaker, add glacial acetic acid stirring and dissolving, then be added thereto to a small amount of acetylacetone,2,4-pentanedione and butyl titanate, continue to stir to well mixed;(2) again to adding appropriate C in step (1) resulting solution after3N4, stirring to C3N4Dispersion is complete, and suspension is poured into evaporating dish, is placed on and precursor powder is obtained in baking oven;(3) precursor powder for obtaining step (2) obtains mesoporous wire metatitanic acid bismuth meal end by calcining.This method is with C3N4It is template, using chemical solution decomposition technique, there is easily-controlled reaction conditions, technique and simple flow, low energy consumption.

Description

One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template
Technical field
The invention belongs to photocatalysis technology field, and in particular to it is a kind of with bismuth nitrate and butyl titanate be bismuth source and titanium Source, with C3N4It is template, the method for preparing wire bismuth titanate photocatalyst.
Background technology
With the development of modern industrial or agricultural, water environment pollution is increasingly severe, the serious prestige of a large amount of organic pollutions in water body The healthy growth of mankind itself or even animals and plants is coerced, water pollution is administered extremely urgent.Photocatalysis technology is a kind of advanced oxidation Technology (AOPs), is particularly in organic wastewater is widely paid close attention in high concentration, the improvement of used water difficult to degradate in recent years.Its In, the focus that one-dimensional material was always studied in recent years due to its substantial amounts of pore structure and high-specific surface area.Also because of these Advantage, the material of this structure has stronger photocatalytic activity.
Bi2O3And TiO2It is compound to form the composite oxides with various crystal phase structures:Bi4Ti3O12, Bi2Ti2O7, Bi2Ti4O11, Bi12TiO20, Bi20TiO32Deng being commonly referred to as metatitanic acid bismuth compound.Metatitanic acid bismuth compound has special crystal structure And electronic structure, there is TiO in their structure6Octahedra or TiO4Tetrahedron, and connected BiOnPolyhedron It is middle to exist because possessing 6s2Lone pair electrons pair and there is the Bi of three-dimensional activity3+Ion, this allows for it, and there is good photocatalysis to live Property.Xu etc. (Acta.Chimica.Sinica, 2005,63 (1), 5) is by the bismuth nitrate of certain mol proportion and the fourth liposoluble solution of metatitanic acid four In acetum, the presoma of bismuth titanates is obtained by chemical solution decomposition technique, then calcined at 550 DEG C, be prepared for Bi12TiO20, Bi4Ti3O12, Bi2Ti2O7Nano-powder.Wang etc. (Mater.Lett, 2014,121 (2), 22) by bismuth nitrate and The fourth fat of metatitanic acid four is dissolved in dimethoxy-ethanol and sodium hydrate aqueous solution, and 20h is reacted at 180 DEG C by solvent-thermal method, It is prepared for Bi4Ti3O12Nanometer sheet.Hou etc. (Nanoscale, 2013,5 (5), 2028) dissolves bismuth nitrate and butyl titanate In DMF, with PVP as surfactant, mesoporous Bi is obtained by method of electrostatic spinning4Ti3O12Nanofiber.But these sides Bismuth titanates obtained in method, its specific surface area is only 10m2g-1, and step is all more complicated, takes and high cost, and these are all Limit the large-scale production and its extensive use in practical systems of bismuth titanates.So exploitation is simple to operate, it is with low cost, Method suitable for mass producing, has become the main target that the porous bismuth titanate photocatalysis preparation producers are pursued.
The content of the invention
It is an object of the present invention to provide one kind with C3N4For template prepares the mesoporous wire bismuth titanates with good photocatalytic activity The method of photochemical catalyst.
The present invention is realized by following steps:
(1) a certain amount of bismuth nitrate is weighed in beaker, adds glacial acetic acid stirring and dissolving, then be added thereto to acetylacetone,2,4-pentanedione With butyl titanate, continue to stir to well mixed;
(2) to adding C in step (1) resulting solution3N4, stirring to C3N4Dispersion is complete, and suspension is poured into evaporating dish In, it is placed on and precursor powder is obtained in baking oven;
(3) precursor powder for obtaining step (2) obtains mesoporous wire metatitanic acid bismuth meal end by calcining.Step (1) In, the bismuth nitrate is 4 with the mol ratio of butyl titanate:3;The volume of the glacial acetic acid, butyl titanate and acetylacetone,2,4-pentanedione Than being 20:0.52:(0.1-0.5).
Butyl titanate and C in step (2) in step (1)3N4Mass ratio be 1:10.
In step (2), the temperature range of baking oven evaporation is 140~180 DEG C, 5~10h of reaction time.
In step (3), the calcining heat is 450~550 DEG C, and heating rate is 2.5~5 DEG C/min, and calcination time is 0.5~4h.
Porous bismuth titanate obtained by the present invention is Ca-Ti ore type, and completely, pattern is regular, good dispersion for crystallization.
Using X-ray diffractometer (XRD), SEM (SEM), transmission electron microscope (TEM), full-automatic thing Physicochemical Sorption Analyzer (BET) isothermal adsorption patterns survey specific surface area and micromorphology analysis are carried out to product, molten with rhodamine B Liquid carries out photocatalytic degradation experiment for target dyestuff, and absorbance is measured by ultraviolet-visible spectrophotometer, is urged with assessing its light Change activity.
The present invention has advantages below:
(1) this method is with C3N4It is template, using chemical solution decomposition technique, with easily-controlled reaction conditions, technique and flow The easy, advantage of low energy consumption.
(2) the mesoporous wire bismuth titanates prepared with the method, possesses pattern rule, even aperture distribution, specific surface area be big, The advantages of photocatalysis effect is good.
Brief description of the drawings
Fig. 1 is the XRD diffraction spectrograms of prepared mesoporous wire bismuth titanates, and diffraction maximum is perovskite bismuth titanates feature in figure Diffraction maximum.
Fig. 2 is the scanning figure a and transmission electron microscope photo b of prepared mesoporous wire bismuth titanates.
Fig. 3 is the nitrogen adsorption desorption figure of prepared mesoporous wire bismuth titanates.
Fig. 4 is business P25 and the when m- degradation rate graph of a relation of mesoporous wire bismuth titanates photocatalytic degradation rhodamine B solution.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
20mL glacial acetic acid solutions are added in the beaker of 50mL, 1g bismuth nitrates are added, magnetic agitation to dissolving, with micro Injector is separately added into 0.1mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, after question response thing is well mixed, adds 5g C3N4, continue to stir to C3N4Dispersion is complete.Gained mixture is poured into evaporating dish, 140 DEG C of evaporation 8h.By the powder of gained It is placed in crucible, 2.5 DEG C/min is warmed up to 550 DEG C, and is incubated 4h.
Fig. 1 is the XRD diffraction spectrograms of obtained sample, contrast standard JCPDS cards (21-1272), it may be determined that be knot The good perovskite Bi of crystalline substance4Ti3O12Powder;Fig. 2 is scanning nuclear microprobe photo, is clear that from figure substantially Linear structure;Fig. 3 is that nitrogen adsorption is desorbed figure, is classified according to IUPAC, and its adsorption isotherm meets IV types, illustrates wherein to deposit In obvious meso-hole structure.
Embodiment 2
20mL glacial acetic acid solutions are added in the beaker of 50mL, 1g bismuth nitrates are added, magnetic agitation to dissolving, with micro Injector is separately added into 0.5mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, after question response thing is well mixed, adds 5g C3N4, continue to stir to C3N4Dispersion is complete.Gained mixture is poured into evaporating dish, 140 DEG C of evaporation 8h.By the powder of gained It is placed in crucible, 2.5 DEG C/min is warmed up to 450 DEG C, and is incubated 4h.
Embodiment 3
20mL glacial acetic acid solutions are added in the beaker of 50mL, 1g bismuth nitrates are added, magnetic agitation to dissolving, with micro Injector is separately added into 0.1mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, after question response thing is well mixed, adds 5g C3N4, continue to stir to C3N4Dispersion is complete.Gained mixture is poured into evaporating dish, 180 DEG C of evaporation 10h.By the powder of gained It is placed in crucible, 5 DEG C/min is warmed up to 450 DEG C, and is incubated 0.5h.
Embodiment 4
20mL glacial acetic acid solutions are added in the beaker of 50mL, 1g bismuth nitrates are added, magnetic agitation to dissolving, with micro Injector is separately added into 0.3mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, after question response thing is well mixed, adds 5g C3N4, continue to stir to C3N4Dispersion is complete.Gained mixture is poured into evaporating dish, 140 DEG C of evaporation 8h.By the powder of gained It is placed in crucible, 3 DEG C/min is warmed up to 450 DEG C, and is incubated 1h.
Embodiment 5
(1) compound concentration is the rhodamine B solution of 10mg/L, and the solution that will be prepared is placed in dark place.
(2) the bismuth titanates 0.1g of preparation is weighed, is placed in Photoreactor, the rhodamine for adding 100mL steps (1) to be prepared B solution, magnetic agitation 30min, bubbling, dark reaction 1h after bismuth titanates is uniformly dispersed, opens water source, and light source carries out photocatalysis Degradation experiment.
(3) sampled once per 30min, sampling amount is 5ml, with many pipe support autobalance centrifuge 3min, makes catalysis Agent is precipitated completely, and the measurement of UV-visible absorbance is used for after centrifugation.
(4) mesoporous wire bismuth titanates prepared as seen from Figure 4 has excellent photocatalytic activity, reacts 30min, to dye The degradation rate of material has reached 30%, and close to 100%, its performance is better than P25 to illumination 180min degradation rates.

Claims (5)

1. one kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, it is characterised in that comprise the following steps:
(1) a certain amount of bismuth nitrate is weighed in beaker, adds glacial acetic acid stirring and dissolving, then be added thereto to acetylacetone,2,4-pentanedione and titanium Sour four butyl esters, continue to stir to well mixed;
(2) to adding C in step (1) resulting solution3N4, stirring to C3N4Dispersion is complete, and suspension is poured into evaporating dish, places Precursor powder is obtained in baking oven;
(3) precursor powder for obtaining step (2) obtains mesoporous wire metatitanic acid bismuth meal end by calcining.
2. one kind according to claim 1 is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, it is characterised in that In step (1), the bismuth nitrate is 4 with the mol ratio of butyl titanate:3;The glacial acetic acid, butyl titanate and acetylacetone,2,4-pentanedione Volume ratio be 20:0.52:(0.1-0.5).
3. one kind according to claim 1 is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, it is characterised in that Butyl titanate and C in step (2) in step (1)3N4Mass ratio be 1:10.
4. one kind according to claim 1 is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, it is characterised in that In step (2), the temperature range of baking oven evaporation is 140~180 DEG C, 5~10h of reaction time.
5. one kind according to claim 1 is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, it is characterised in that In step (3), the calcining heat is 450~550 DEG C, and heating rate is 2.5~5 DEG C/min, and calcination time is 0.5~4h.
CN201710107373.2A 2017-02-27 2017-02-27 One kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template Expired - Fee Related CN106915771B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110871101A (en) * 2019-12-12 2020-03-10 肇庆学院 Preparation and application of mesoporous carbon-bismuth titanate composite photocatalytic material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101428210A (en) * 2008-12-12 2009-05-13 上海师范大学 Porous structured bismuth titanate microsphere, preparation method and application thereof
CN104005089A (en) * 2013-02-27 2014-08-27 吉林师范大学 Preparation method for self-assembled Bi4Ti3O12 single-crystal nanowire by solvent process
CN104211116A (en) * 2014-08-26 2014-12-17 浙江大学 Preparation method of Bi4Ti3O12 single-crystal nanorod and Bi4Ti3O12 single-crystal nanorod product
CN104556240A (en) * 2015-02-04 2015-04-29 西安工业大学 Preparation method of bismuth titanate (BT) ferroelectric film
CN105521776A (en) * 2014-09-29 2016-04-27 南京理工大学 Compound metal oxide Bi4Ti3O12 nanocrystal and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101428210A (en) * 2008-12-12 2009-05-13 上海师范大学 Porous structured bismuth titanate microsphere, preparation method and application thereof
CN104005089A (en) * 2013-02-27 2014-08-27 吉林师范大学 Preparation method for self-assembled Bi4Ti3O12 single-crystal nanowire by solvent process
CN104211116A (en) * 2014-08-26 2014-12-17 浙江大学 Preparation method of Bi4Ti3O12 single-crystal nanorod and Bi4Ti3O12 single-crystal nanorod product
CN105521776A (en) * 2014-09-29 2016-04-27 南京理工大学 Compound metal oxide Bi4Ti3O12 nanocrystal and preparation method thereof
CN104556240A (en) * 2015-02-04 2015-04-29 西安工业大学 Preparation method of bismuth titanate (BT) ferroelectric film

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KUNQIAN等: "Constructing mesoporousBi4Ti3O12 with enhanced visible light photocatalytic activity", 《MATERIALS LETTERS》 *
LINGDONG KONG等: "Mesoporous bismuth titanate with visible-light photocatalytic activity", 《CHEM. COMMUN.》 *
XUE LIN等: "Bismuth titanate microspheres: Directed synthesis and their visible light photocatalytic activity", 《APPLIED SURFACE SCIENCE》 *
李艳杰等: "Bi4Ti3012的熔盐法制备及改性研究进展", 《材料导报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110871101A (en) * 2019-12-12 2020-03-10 肇庆学院 Preparation and application of mesoporous carbon-bismuth titanate composite photocatalytic material
CN110871101B (en) * 2019-12-12 2022-09-16 肇庆学院 Preparation and application of mesoporous carbon-bismuth titanate composite photocatalytic material

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