CN107376900A - The preparation method and applications of bismuth molybdate ultrathin nanometer piece catalysis material - Google Patents

The preparation method and applications of bismuth molybdate ultrathin nanometer piece catalysis material Download PDF

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CN107376900A
CN107376900A CN201710615500.XA CN201710615500A CN107376900A CN 107376900 A CN107376900 A CN 107376900A CN 201710615500 A CN201710615500 A CN 201710615500A CN 107376900 A CN107376900 A CN 107376900A
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moo
preparation
ultrathin nanometer
nanometer piece
catalysis material
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张子重
谢琰玉
王绪绪
龙金林
员汝胜
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Fuzhou University
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Fuzhou 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
    • 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/31Chromium, molybdenum or tungsten combined with 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
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30
    • B01J35/39
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst

Abstract

The invention discloses a kind of preparation method and applications of bismuth molybdate ultrathin nanometer piece catalysis material, its preparation method is:1)Bi2MoO6The preparation of the predecessor of ultrathin nanometer piece:By a certain amount of Na2MoO4·2H2O is dissolved in a certain amount of deionized water, adds a certain amount of CTAB under agitation, and Bi (NO are stoichiometrically added after being sufficiently stirred3)3·5H2O, it is thoroughly mixed uniformly;2) it is 90 180 DEG C in temperature, the 24h of predecessor hydro-thermal reaction 6;Then product centrifuged, washed, the air drying at 60 DEG C, Bi is made2MoO6Ultrathin nanometer piece.The present invention have the advantages that hydro-thermal prepare, be not required to it is surface protonated, be not required to regulation pH, simple to operate, yield is high and versatile.The photochemical catalyst has efficient photocatalysis to selectively reduction nitrobenzene compound performance.

Description

The preparation method and applications of bismuth molybdate ultrathin nanometer piece catalysis material
Technical field
The invention belongs to catalysis technical field, and in particular to a kind of preparation side of bismuth molybdate ultrathin nanometer piece catalysis material Method and its application.
Background technology
Since graphene is found, two-dimension nano materials turn into important research object as current active material.Two Dimension nano material has the microstructure and physical and chemical performance that corresponding body phase material do not possess.It is not only able to the intrinsic of strengthening material Can, while also there is the special natures such as higher than surface, thermal conductivity is good, mechanical strength is big.Two-dimension nano materials can specificity exposure Active crystal face, there is higher ratio surface, be advantageous to increase avtive spot, promote electric charge in semiconductor and the contact surface of reactant Aggregation is participated in light-catalyzed reaction.Two-dimension nano materials receive significant attention because of its outstanding light-catalyzed reaction performance.It is existing It is that liquid phase is peeled off preparing the most important method of two-dimensional nano sheet material, is only applicable to the stratiform formed by Van der Waals force stacking Crystal, such as graphene, chalcogen compound.The preparation method of study two-dimensional ultrathin oxide nanometer sheet, for enriching two-dimentional material It is an important breakthrough for material.
Bi2MoO6It is the composite oxides of typical Aurivillius types layer structure, has significantly in visible region Absorb, there is the ability of visible light catalytic oxidation processing organic pollution.Again because its catalysis material has higher chemistry steady The advantages that qualitative and nontoxic, numerous focus of attention are caused in recent ten years, and achieve certain achievement in research.Meanwhile Bi2MoO6Crystal is by Bi2O2Layer and MoO6Octahedral structure lamella is alternately arranged composition, and this lamellar structure has larger ratio Surface area and unique Electronic Structure.But Bi2MoO6Interlayer closely connected by strong Bi-O keys, and existing biography can not be used System liquid phase stripping method largely prepares single-layer sheet nano material.Liquid phase stripping method prepares Bi2MoO6Process be present and answer in ultrathin nanometer piece It is miscellaneous, long preparation period, the problems such as nanometer sheet product is in uneven thickness.
In summary, the simple efficient new method of research, which prepares oxide ultrathin nanometer sheet material, has highly important meaning Justice.Through consulting literatures, it has been found that there is presently no assist self assembly to prepare Bi using CTAB2MoO6The correlation of ultrathin nanometer piece Report.
The content of the invention
It is an object of the invention to provide a kind of Bi2MoO6The preparation method of ultrathin nanometer piece catalysis material.This method without Prolonged liquid phase is needed to peel off, using cetyl trimethylammonium bromide(CTAB)Mixed with reaction raw materials, in lower temperature Sample is can obtain under hydrothermal reaction condition.This method reaction condition is gentle, simple to operation, obtained Bi2MoO6It is ultra-thin to receive Rice piece has remarkable photocatalysis performance.
To achieve the above object, the present invention is achieved by the following technical solutions:
A kind of Bi2MoO6The preparation method of ultrathin nanometer piece catalysis material, described Bi2MoO6Nanometer sheet be thickness 10nm with Under two-dimensional ultrathin nanometer sheet, thickness most I is half of unit cell dimension, is comprised the following steps
(1)By 0.1 ~ 5 mmol Na2MoO4·2H2O is dissolved in 80 mL deionized waters, and stirring is allowed to fully dissolve, and obtains Na2MoO4·2H2The O aqueous solution;
(2)By 0.1-10.0 mmol cetyl trimethylammonium bromides(CTAB)Add step(1)Gained Na2MoO4·H2O is molten In liquid, stirring to dissolving;
(3)Stoichiometrically to step(2)Add 0.2-10.0 mmol Bi (NO in resulting solution3)3·5H2O, stir 0.5- 1h;
(4)By step(3)Middle gained ecru suspension is transferred in 100mL autoclaves, and hydro-thermal is anti-at 90-180 DEG C 6-24h is answered, gained sediment obtains Bi through centrifuging, washing, dry2MoO6Ultrathin nanometer piece.
Present invention proposition is under CTAB synergisms, Bi2MoO6By Br therein-Control self assembly hydro-thermal synthetic time series surpass Thin nanometer sheet.The Bi prepared using the present invention2MoO6Ultrathin nanometer piece, it is applied to photocatalysis to selectively reduction nitro class Compound.Experimentation is as follows:By 30 mg Bi2MoO6It is dispersed in and is loaded with the reaction bulb of 10 mL nitrobenzene.By reaction bulb in It is sufficiently stirred at lucifuge and is passed through a large amount of nitrogen for a period of time, catalyst surface p-nitrophenyl is reached absorption-desorption equilibrium.So After lower Xe light irradiations are stirred at room temperature, a certain amount of reaction solution centrifugation, filtering are regularly taken, with 10 times of dilution in acetonitrile, determines it The conversion ratio of middle nitrobenzene.
Bi2MoO6The physical property characterizing method of ultrathin nanometer piece catalysis material:Use X-ray diffraction(XRD)Spectrum analysis Product materials form and structure situation, use field emission scanning electron microscope(FESEM)The pattern of product is observed, is diffused with UV-Vis The light absorbs situation of (DRS) analysis product is composed, uses transmission electron microscope(TEM)The crystal structure of product is analyzed, product is analyzed with BET Specific surface area.
The beneficial effects of the present invention are:Bi of the present invention2MoO6The preparation method of ultrathin nanometer piece catalysis material It is simple and easy to do, be not required to it is surface protonated and regulation reaction solution pH, can by change hydro-thermal reaction temperature and the reaction time and The thickness of CTAB amount regulation nanometer sheet is added, to obtain the Bi of specific morphology2MoO6Ultrathin nanometer piece catalysis material.
Brief description of the drawings
Fig. 1 is the XRD spectra that product is made in embodiment 1 and comparative example;
Fig. 2 is the DRS spectrograms of product obtained by embodiment 1 and comparative example;
Fig. 3 is Bi obtained by comparative example2MoO6Nanocrystalline TEM photos;
Fig. 4 is Bi obtained by embodiment 1 ~ 42MoO6The TEM photos of nanometer sheet;
Fig. 5 is Bi obtained by embodiment 1 and comparative example2MoO6BET figure;
Fig. 6 is Bi obtained by embodiment 1 and comparative example2MoO6AFM figure;
Fig. 7 is Bi obtained by the embodiment 1 and comparative example described in application examples2MoO6Photocatalysis to selectively reduction nitrobenzene conversion Rate figure;
Fig. 8 is Bi obtained by the embodiment 1 and comparative example described in application examples2MoO6Photocatalysis to selectively reduction nitrobenzene activity Figure;
Fig. 9 is comparative example, the Bi obtained by embodiment 1 ~ 52MoO6XRD spectra.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Comparative example
By 2.5 mmol Na2MoO4·2H2O is dissolved in 80ml deionized waters, is sufficiently stirred and is allowed to dissolve;Then 5 mmol are added Bi(NO3)3·5H2O, stir 30min;Above-mentioned resulting solution is transferred in 100 mL reactors, in 100 DEG C of h of hydro-thermal reaction 24; Question response terminates to be cooled to room temperature, and precipitated product is centrifuged, washed, and is then completely dried at 60 DEG C, obtains Bi2MoO6Nanometer Particle(Shown in Fig. 3), its light absorption characteristics is as shown in Figure 2.
Embodiment 1
By 2.5 mmol Na2MoO4·2H2O is dissolved in 80ml deionized waters, is sufficiently stirred and is allowed to dissolve;Then by 5 mmol's CTAB adds Na under agitation2MoO4In solution, it is sufficiently stirred and is allowed to dissolve, is well mixed;Then 5 mmol Bi are added (NO3)3·5H2O, stir 30min;Above-mentioned resulting solution is transferred in 100 mL reactors, in 90 DEG C of h of hydro-thermal reaction 24;Treat Reaction end is cooled to room temperature, and precipitated product is centrifuged, washed, is then completely dried at 60 DEG C, obtains Bi2MoO6It is ultra-thin to receive Rice piece(As shown in the A in Fig. 4), obtained Bi2MoO6Ultrathin nanometer piece has higher crystallinity(As shown in Figure 1), its light absorbs Feature is as shown in Figure 2.
Embodiment 2
By 2.5 mmol Na2MoO4·2H2O is dissolved in 80ml deionized waters, is sufficiently stirred and is allowed to dissolve;Then by 5 mmol's CTAB adds Na under agitation2MoO4In solution, it is sufficiently stirred and is allowed to dissolve, is well mixed;Then 5 mmol Bi are added (NO3)3·5H2O, stir 30min;Above-mentioned resulting solution is transferred in 100 mL reactors, in 100 DEG C of h of hydro-thermal reaction 24;Treat Reaction end is cooled to room temperature, and precipitated product is centrifuged, washed, is then completely dried at 60 DEG C, obtains Bi2MoO6It is ultra-thin to receive Rice piece(As shown in the B in Fig. 4), its average thickness is in 1nm or so.
Embodiment 3
By 2.5 mmol Na2MoO4·2H2O is dissolved in 80ml deionized waters, is sufficiently stirred and is allowed to dissolve;Then by 5 mmol's CTAB adds Na under agitation2MoO4In solution, it is sufficiently stirred and is allowed to dissolve, is well mixed;Then 5 mmol Bi are added (NO3)3·5H2O, stir 30min;Above-mentioned resulting solution is transferred in 100 mL reactors, in 120 DEG C of h of hydro-thermal reaction 24;Treat Reaction end is cooled to room temperature, and precipitated product is centrifuged, washed, is then completely dried at 60 DEG C, obtains Bi2MoO6Still it is super Thin nanometer sheet(As shown by c in fig 4).
Embodiment 4
By 2.5 mmol Na2MoO4·2H2O is dissolved in 80ml deionized waters, is sufficiently stirred and is allowed to dissolve;Then by 5 mmol's CTAB adds Na under agitation2MoO4In solution, it is sufficiently stirred and is allowed to dissolve, is well mixed;Then 5 mmol Bi are added (NO3)3·5H2O, stir 30min;Above-mentioned resulting solution is transferred in 100 mL reactors, in 140 DEG C of h of hydro-thermal reaction 24;Treat Reaction end is cooled to room temperature, and precipitated product is centrifuged, washed, then at 60 DEG C, is completely dried, obtains Bi2MoO6Still it is Ultrathin nanometer piece(As shown in the D in Fig. 4).
Embodiment 5
By 2.5 mmol Na2MoO4·2H2O is dissolved in 80ml deionized waters, is sufficiently stirred and is allowed to dissolve;Then by 5 mmol's CTAB adds Na under agitation2MoO4In solution, it is sufficiently stirred and is allowed to dissolve, is well mixed;Then 5 mmol Bi are added (NO3)3·5H2O, stir 30min;Above-mentioned resulting solution is transferred in 100 mL reactors, in 160 DEG C of h of hydro-thermal reaction 24;Treat Reaction end is cooled to room temperature, and precipitated product is centrifuged, washed, is then completely dried at 60 DEG C, obtains Bi2MoO6Still it is super Thin nanometer sheet.
Application examples
To above-mentioned gained Bi2MoO6Ultrathin nanometer piece catalysis material carries out answering for photocatalysis to selectively reduction nitro compound With:
Take comparative example and the gained catalyst 30mg of embodiment 1 to add in reaction bulb respectively, add 10mL nitrobenzene compounds. Reaction bulb is stirred to 1 h under the conditions of lucifuge, catalyst surface p-nitrophenyl is reached absorption-desorption equilibrium.Then in room temperature Under stirring, with Xe light irradiation certain times.A certain amount of reaction solution centrifugation is regularly pipetted in During Illumination, takes the upper strata after centrifugation Liquid filters, with 10 times of dilution in acetonitrile.Then the aniline in high performance liquid chromatography detection product is used.When reacting 40min, Bi2MoO6It is super The activity of the photo catalytic reduction nitrobenzene of thin nanometer sheet is nanocrystalline 4 times(As shown in Figure 7).As a result show, using the present invention The Bi of preparation2MoO6Ultrathin nanometer piece has excellent photocatalytic activity.Presently preferred embodiments of the present invention is the foregoing is only, it is all The equivalent changes and modifications done according to scope of the present invention patent, it should all belong to the covering scope of the present invention.

Claims (6)

  1. A kind of 1. Bi2MoO6The preparation method of ultrathin nanometer piece catalysis material, it is characterised in that:Comprise the following steps:
    (1)By Na2MoO4·2H2O is dissolved in deionized water, is sufficiently stirred and is allowed to dissolve, obtains Na2MoO4·2H2The O aqueous solution;
    (2)Cetyl trimethylammonium bromide is added into step(1)Gained Na2MoO4·H2In the O aqueous solution, stirring to dissolving; (3)Stoichiometrically to step(2)Bi (NO are added in resulting solution3)3·5H2O, then stir 0.5-1h;(4)By step (3)Middle gained ecru suspension, which is transferred in autoclave, carries out hydro-thermal reaction, and gained is precipitated through centrifuging, washing and do It is dry, produce Bi2MoO6Ultrathin nanometer piece, the thickness of gained nanometer sheet is in below 10nm.
  2. 2. Bi according to claim 12MoO6The preparation method of ultrathin nanometer piece catalysis material, it is characterised in that:Step (1)The Na2MoO4·2H2O addition is 0.1 ~ 5 mmol, deionized water 80mL.
  3. 3. Bi according to claim 12MoO6The preparation method of ultrathin nanometer piece catalysis material, it is characterised in that:Step (2)The addition of the cetyl trimethylammonium bromide is 0.1 ~ 10mmol.
  4. 4. Bi according to claim 12MoO6The preparation method of ultrathin nanometer piece catalysis material, it is characterised in that:Step (3)Bi (the NO3)3·5H2O addition is 0.2 ~ 10mmol.
  5. 5. Bi according to claim 12MoO6The preparation method of ultrathin nanometer piece catalysis material, it is characterised in that:Step Suddenly(4)The hydrothermal temperature is 90-180 DEG C, reaction time 6-24h.
  6. A kind of 6. Bi made from preparation method as claimed in claim 12MoO6The application of ultrathin nanometer piece, it is characterised in that:Institute The Bi stated2MoO6The ultrathin nanometer piece catalyst reduction nitro compound of photocatalysis to selectively at room temperature.
CN201710615500.XA 2017-07-26 2017-07-26 The preparation method and applications of bismuth molybdate ultrathin nanometer piece catalysis material Pending CN107376900A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940366A (en) * 2018-06-28 2018-12-07 华南理工大学 A kind of duct can modulation Fe Base Metal organic backbone-phosphotungstic acid preparation method
CN109569735A (en) * 2018-11-29 2019-04-05 南昌航空大学 A kind of bismuth series photocatalyst and its preparation method and application
CN110498487A (en) * 2019-09-06 2019-11-26 西安建筑科技大学 A kind of preparation method, product and its application of the modified bismuth molybdate optoelectronic pole of cetyl trimethylammonium bromide
CN111804295A (en) * 2019-04-12 2020-10-23 中国科学技术大学 Method for preparing oxygen vacancy-containing bismuth tungstate ultrathin slice, oxygen vacancy-containing bismuth tungstate ultrathin slice and application thereof
CN111905715A (en) * 2020-06-22 2020-11-10 江苏中江材料技术研究院有限公司 Plasma-induced Bi2MoO6Method for preparing photocatalyst
CN112209448A (en) * 2020-08-27 2021-01-12 南京邮电大学 Ultra-small FeS nanodot and preparation method and application thereof
CN113441132A (en) * 2021-06-10 2021-09-28 南昌航空大学 Preparation method of high-activity bismuth molybdate/biochar composite photocatalyst based on strong interface interaction
CN113856703A (en) * 2021-10-15 2021-12-31 泉州师范学院 Indium zinc sulfide and bismuth molybdate nanosheet composite photocatalyst with nanoflower structure and preparation method and application thereof
CN114210322A (en) * 2021-12-21 2022-03-22 辽宁大学 Bi0/Bi2MoO6{010} wave-absorbing material with high exposure {010} crystal face, preparation method and application
CN114335501A (en) * 2021-12-31 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon-coated bismuth molybdate nanosheet negative electrode material

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* Cited by examiner, † Cited by third party
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KAIQIANG JING等: "Development and photocatalytic mechanism of monolayer Bi2MoO6 nanosheets for the selective oxidation of benzylic alcohols", 《CHEM. COMMUN.》 *
吴伟明: "硝基苯类有机物的光催化加氢及其机理研究", 《中国博士学位论文全文数据库》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940366A (en) * 2018-06-28 2018-12-07 华南理工大学 A kind of duct can modulation Fe Base Metal organic backbone-phosphotungstic acid preparation method
CN109569735A (en) * 2018-11-29 2019-04-05 南昌航空大学 A kind of bismuth series photocatalyst and its preparation method and application
CN111804295A (en) * 2019-04-12 2020-10-23 中国科学技术大学 Method for preparing oxygen vacancy-containing bismuth tungstate ultrathin slice, oxygen vacancy-containing bismuth tungstate ultrathin slice and application thereof
CN110498487A (en) * 2019-09-06 2019-11-26 西安建筑科技大学 A kind of preparation method, product and its application of the modified bismuth molybdate optoelectronic pole of cetyl trimethylammonium bromide
CN110498487B (en) * 2019-09-06 2021-12-24 西安建筑科技大学 Preparation method of cetyl trimethyl ammonium bromide modified bismuth molybdate photoelectrode, product and application thereof
CN111905715A (en) * 2020-06-22 2020-11-10 江苏中江材料技术研究院有限公司 Plasma-induced Bi2MoO6Method for preparing photocatalyst
CN112209448B (en) * 2020-08-27 2023-04-07 南京邮电大学 Ultra-small FeS nanodot and preparation method and application thereof
CN112209448A (en) * 2020-08-27 2021-01-12 南京邮电大学 Ultra-small FeS nanodot and preparation method and application thereof
CN113441132A (en) * 2021-06-10 2021-09-28 南昌航空大学 Preparation method of high-activity bismuth molybdate/biochar composite photocatalyst based on strong interface interaction
CN113856703A (en) * 2021-10-15 2021-12-31 泉州师范学院 Indium zinc sulfide and bismuth molybdate nanosheet composite photocatalyst with nanoflower structure and preparation method and application thereof
CN113856703B (en) * 2021-10-15 2023-12-29 泉州师范学院 Indium zinc sulfide and bismuth molybdate nano-sheet composite photocatalyst with nano-flower structure, and preparation method and application thereof
CN114210322A (en) * 2021-12-21 2022-03-22 辽宁大学 Bi0/Bi2MoO6{010} wave-absorbing material with high exposure {010} crystal face, preparation method and application
CN114210322B (en) * 2021-12-21 2023-05-26 辽宁大学 Bi0/Bi2MoO6{010} wave-absorbing material with high exposure {010} crystal face, preparation method and application
CN114335501A (en) * 2021-12-31 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon-coated bismuth molybdate nanosheet negative electrode material

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