CN106915771B - 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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CN106915771B
CN106915771B CN201710107373.2A CN201710107373A CN106915771B CN 106915771 B CN106915771 B CN 106915771B CN 201710107373 A CN201710107373 A CN 201710107373A CN 106915771 B CN106915771 B CN 106915771B
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bismuth
mesoporous
wire
template
prepared
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CN106915771A (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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Abstract

The present invention provides one kind with C3N4The method that mesoporous wire bismuth titanates is prepared for template, step are as follows:(1) a certain amount of bismuth nitrate is weighed in beaker, adds in glacial acetic acid stirring and dissolving, then adds in a small amount of acetylacetone,2,4-pentanedione and butyl titanate thereto, continues to stir to uniformly mixed;(2) after appropriate C is added in into step (1) acquired solution again3N4, stir to C3N4It is scattered complete, suspension is poured into evaporating dish, is placed in baking oven and precursor powder is made;(3) precursor powder that step (2) obtains is obtained into mesoporous wire metatitanic acid bismuth meal end by calcining.This method is with C3N4For 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 fields, and in particular to one kind is using bismuth nitrate and butyl titanate as bismuth source and titanium Source, with C3N4For 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, it is extremely urgent to administer water pollution.Photocatalysis technology is a kind of advanced oxidation Technology (AOPs), in recent years organic wastewater be particularly high concentration, used water difficult to degradate improvement in widely paid close attention to.Its In, hot spot 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 have stronger photocatalytic activity.
Bi2O3And TiO2It is compound to form the composite oxides with a variety of 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 are TiO in their structure6Octahedra or TiO4Tetrahedron, and connected BiOnPolyhedron It is middle to exist because possessing 6s2Lone pair electrons pair and with the Bi of three-dimensional activity3+Ion, this allows for it and lives with good photocatalysis Property.Xu etc. (Acta.Chimica.Sinica, 2005,63 (1), 5) is by four fourth liposoluble solution of the bismuth nitrate of certain mol proportion and metatitanic acid In acetum, the presoma of bismuth titanates is obtained by chemical solution decomposition technique, then is calcined at 550 DEG C, is prepared for Bi12TiO20, Bi4Ti3O12, Bi2Ti2O7Nano-powder.Wang etc. (Mater.Lett, 2014,121 (2), 22) by bismuth nitrate and Four fourth fat of metatitanic acid is dissolved in dimethoxy-ethanol and sodium hydrate aqueous solution, reacts 20h at 180 DEG C by solvent-thermal method, It is prepared for Bi4Ti3O12Nanometer sheet.Hou etc. (Nanoscale, 2013,5 (5), 2028) bismuth nitrate and butyl titanate are dissolved In DMF, using PVP as surfactant, mesoporous Bi has been made by method of electrostatic spinning4Ti3O12Nanofiber.However these sides Bismuth titanates made from method, specific surface area are only 10m2g-1, and step is all more complicated, takes and of high cost, these are all The large-scale production and its extensive use in practical systems for limiting bismuth titanates.So exploitation is easy to operate, it is of low cost, Suitable for the method for large-scale production, have 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 C3N4The mesoporous wire bismuth titanates with good photocatalytic activity is prepared for template The method of photochemical catalyst.
The present invention is realized by following steps:
(1) a certain amount of bismuth nitrate is weighed in beaker, is added in glacial acetic acid stirring and dissolving, then is added in acetylacetone,2,4-pentanedione thereto With butyl titanate, continue to stir to uniformly mixed;
(2) C is added in into step (1) acquired solution3N4, stir to C3N4It is scattered complete, suspension is poured into evaporating dish In, it is placed in baking oven and precursor powder is made;
(3) precursor powder that step (2) obtains is obtained into mesoporous wire metatitanic acid bismuth meal end by calcining.Step (1) In, the molar ratio of the bismuth nitrate and butyl titanate is 4:3;The volume of the glacial acetic acid, butyl titanate and acetylacetone,2,4-pentanedione Than for 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 crystallization is complete, pattern rule, good dispersion.
Utilize X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), full-automatic object 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, measures absorbance by ultraviolet-visible spectrophotometer, is urged with assessing its light Change activity.
The present invention has the following advantages:
(1) this method is with C3N4For template, using chemical solution decomposition technique, there is easily-controlled reaction conditions, technique and flow The advantages of simplicity, low energy consumption.
(2) with the method prepare mesoporous wire bismuth titanates, possess pattern rule, even aperture distribution, large specific surface area, The advantages that photocatalysis effect is good.
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 the when m- degradation rate relational graph of business P25 and 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, add 1g bismuth nitrates, for magnetic agitation to dissolving, use is micro Injector is separately added into 0.1mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, treats that reactant after mixing, adds 5g C3N4, continue stirring to C3N4It is scattered 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 warming up to 550 DEG C, and keeps the temperature 4h.
Fig. 1 be sample obtained XRD diffraction spectrograms, contrast standard JCPDS cards (21-1272), it may be determined that for knot The good perovskite Bi of crystalline substance4Ti3O12Powder;Fig. 2 is scanning nuclear microprobe photo, is clear that from figure apparent Linear structure;Fig. 3 is nitrogen adsorption desorption figure, is classified according to IUPAC, adsorption isotherm meets IV types, illustrates wherein to deposit In apparent meso-hole structure.
Embodiment 2
20mL glacial acetic acid solutions are added in the beaker of 50mL, add 1g bismuth nitrates, for magnetic agitation to dissolving, use is micro Injector is separately added into 0.5mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, treats that reactant after mixing, adds 5g C3N4, continue stirring to C3N4It is scattered 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 warming up to 450 DEG C, and keeps the temperature 4h.
Embodiment 3
20mL glacial acetic acid solutions are added in the beaker of 50mL, add 1g bismuth nitrates, for magnetic agitation to dissolving, use is micro Injector is separately added into 0.1mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, treats that reactant after mixing, adds 5g C3N4, continue stirring to C3N4It is scattered complete.Gained mixture is poured into evaporating dish, 180 DEG C of evaporation 10h.By the powder of gained End is placed in crucible, and 5 DEG C/min is warming up to 450 DEG C, and keeps the temperature 0.5h.
Embodiment 4
20mL glacial acetic acid solutions are added in the beaker of 50mL, add 1g bismuth nitrates, for magnetic agitation to dissolving, use is micro Injector is separately added into 0.3mL acetylacetone,2,4-pentanediones and 0.52ml butyl titanates, treats that reactant after mixing, adds 5g C3N4, continue stirring to C3N4It is scattered 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 warming up to 450 DEG C, and keeps the temperature 1h.
Embodiment 5
(1) compound concentration is the rhodamine B solution of 10mg/L, and the solution prepared is placed in dark place.
(2) the bismuth titanates 0.1g of preparation is weighed, is placed in Photoreactor, adds in the rhodamine that 100mL steps (1) are prepared B solution, magnetic agitation 30min, bubbling, dark reaction 1h after bismuth titanates is uniformly dispersed, open water source, and light source carries out photocatalysis Degradation experiment.
(3) per 30min, once, sampling amount 5ml with multitube frame autobalance centrifuge 3min, makes catalysis for sampling Agent precipitates completely, and the measurement of UV-visible absorbance is used for after centrifugation.
(4) prepared mesoporous wire bismuth titanates has excellent photocatalytic activity as seen from Figure 4, reacts 30min, to dye The degradation rate of material has reached 30%, and for illumination 180min degradation rates close to 100%, performance is better than P25.

Claims (4)

1. one kind is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, which is characterized in that comprise the following steps:
(1)A certain amount of bismuth nitrate is weighed in beaker, glacial acetic acid stirring and dissolving is added in, then adds in acetylacetone,2,4-pentanedione and titanium thereto Sour four butyl esters continue to stir to uniformly mixed;
(2)To step(1)C is added in acquired solution3N4, stir to C3N4It is scattered complete, suspension is poured into evaporating dish, is placed Precursor powder is made in baking oven;
(3)By step(2)Obtained precursor powder obtains mesoporous wire metatitanic acid bismuth meal end by calcining;
Step(1)Middle butyl titanate and step(2)Middle C3N4Mass ratio be 1:10.
2. one kind according to claim 1 is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, which is characterized in that Step(1)In, the molar ratio of the bismuth nitrate and butyl titanate is 4:3;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, which is characterized in that Step(2)In, the temperature range of baking oven evaporation is 140 ~ 180 DEG C, 5 ~ 10 h of reaction time.
4. one kind according to claim 1 is with C3N4The method that mesoporous wire bismuth titanates is prepared for template, which is characterized in that Step(3)In, 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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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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