CN107973346B - A kind of method that visible light auxiliary prepares pure hydrogen tungsten bronze - Google Patents

A kind of method that visible light auxiliary prepares pure hydrogen tungsten bronze Download PDF

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CN107973346B
CN107973346B CN201810049772.2A CN201810049772A CN107973346B CN 107973346 B CN107973346 B CN 107973346B CN 201810049772 A CN201810049772 A CN 201810049772A CN 107973346 B CN107973346 B CN 107973346B
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cds
added
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acid solution
thermal reaction
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CN107973346A (en
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刘平
张璐璐
王波
王瑶珠
王凯强
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Fuzhou University
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of novel methods for preparing hydrogen tungsten bronze using visible light catalytic auxiliary, with WCl6For predecessor, solvent thermal reaction is carried out in dehydrated alcohol, obtains W18O49；Again by W18O49It is dispersed in water, cadmium acetate and thioacetamide is added, obtains W through hydro-thermal reaction18O49/CdS；By gained W18O49/ CdS is added in aqueous hydrochloric acid solution, generates H through illuminationxWO3/ CdS compound (0 < x < 1)；Finally be slowly dropped in the nitric acid solution of low concentration and clear up CdS, then it is washed, be dried to obtain simple HxWO3Sample.Preparation method of the present invention have the characteristics that equipment be simple and convenient to operate, synthesizing efficient.

Description

A kind of method that visible light auxiliary prepares pure hydrogen tungsten bronze
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of preparation method of pure hydrogen tungsten bronze.
Background technique
WO3It is had a wide range of applications with its special performance in the fields such as photocatalysis, sensor, photochromic.Pass through to WO3Tungsten bronze prepared by incorporation alkali metal ion, ammonium ion or hydrogen ion is a kind of steady in tunnel structure specific to crystal Qualitative higher, with navy blue metallic luster cation doping metal oxide, generally uses MxWO3It indicates, shows metal The property of conductor or semiconductor, color can pass through the different regulations of M and x from performance.1949, A.Magne li was synthesized WO6Octahedral unit is total to the tungstates K of vertex structurexWO3(0 < x < 1) finds that it has the color and bright property as bronze, therefore The compound of similar this structure is known as tungsten bronze type material.Tungsten bronze type material is in ferroelectricity, piezoelectricity, pyroelectricity, non-linear Optics etc. excellent performance with unique, to gradually receive extensive attention, at present in electronic material research field In have become the second largest electron-like globs of material for being only second to perovskite-type material.
Has the report of some preparation nanometer tungsten bronzes at present, as patent CN 103496744A discloses a kind of reduction-state The synthetic method of ammonium tungsten bronze uses WCl6As tungsten source, oleic acid is added as solvent, W:NH4 +Molar ratio be 1:(0.2 ~0.3), 0.5~48 h of crystallization under 150~350 DEG C of hot conditions, it is final to obtain reduction-state ammonium tungsten bronze nanometer Powder.This method generated time length, low yield, cost are very high, and the infrared absorption performance of gained tungsten bronze material is poor.Specially Sharp CN 104528829A report using tungstate solution by cation exchange obtains wolframic acid colloidal sol, add reducing agent with Caesium source obtains corresponding presoma, and caesium tungsten bronze nanometer can be made by presoma being added to after carrying out hydro-thermal reaction in reaction kettle Salt.This method has used base exchange method during preparing precursor, therefore the amount of single synthesis is limited, and hydro-thermal is closed It is taken a long time at method, needs high-temperature and high-pressure conditions in reaction process, energy consumption is larger and poor repeatability.Therefore, one is also lacked at present The industrialization synthetic method of cheap, reliable, the stable pure nanometer tungsten bronze of the synthesis especially hydrogen tungsten bronze of kind, this problem have become To restrict its widely applied bottleneck.
Summary of the invention
A kind of method for assisting preparing pure hydrogen tungsten bronze the purpose of the present invention is to provide visible light, uses W18O49With The compound of CdS quickly obtains H under the auxiliary of visible light and hydrochloric acid as presomaxWO3/ CdS compound recycles low dense The nitric acid of degree clears up CdS, to obtain pure HxWO3Sample.There is this method preparation condition to require, and low, easy to operate, synthesis is high Effect and the stable feature of properties of product.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of method that visible light auxiliary prepares pure hydrogen tungsten bronze comprising following steps:
(1) with WCl6As predecessor, dehydrated alcohol is solvent, is obtained through 100-200 DEG C of solvent thermal reaction 10-40h W18O49；
(2) by gained W18O49It is dispersed in water, and cadmium acetate and thioacetamide is added, through 100-200 DEG C of hydro-thermal reaction 10-30h obtains W18O49/CdS；Wherein, the molar ratio of cadmium acetate and thioacetamide is 1.6:1, gained W18O49In/CdS W18O49Mass ratio with CdS is 1:1-1:15；
(3) by gained W18O49/ CdS is added in the aqueous hydrochloric acid solution that volumetric concentration is 5-10%, in sunlight or xenon lamp 0.5-3h is irradiated under equal artificial light sources, obtains HxWO3/ CdS compound (0 < x < 1)；
(4) by gained HxWO3/ CdS compound is added drop-wise in the low concentration nitric acid solution that volumetric concentration is 25-35%, stirring 1h clears up CdS sufficiently, then pure H is made in washed, dryingxWO3。
The present invention uses W18O49Compound with CdS quickly obtains under the auxiliary of visible light and hydrochloric acid as presoma HxWO3/ CdS compound recycles the nitric acid of low concentration to clear up CdS, to obtain pure HxWO3Sample；The requirement of its preparation condition Low, easy to operate, synthesizing efficient, and product good dispersion.
Detailed description of the invention
Fig. 1 is 1 products therefrom H of embodimentxWO3X ray diffracting spectrum.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
Weigh 200mg WCl6, be added 50mL dehydrated alcohol in, in 200 DEG C insulation reaction 24 hours, through ethyl alcohol and washing It is 12 hours dry at 60 DEG C after washing, obtain W18O49；Weigh gained W18O4940mg is scattered in 60mL H2In O, it is added 0.148g cadmium acetate and 0.03g thioacetamide, in 150 DEG C hydro-thermal insulation reaction 20 hours, obtain W18O49/CdS；Weigh institute Obtain W18O49/ CdS 200mg is added in the mixed solution of 45mL water and 3mL hydrochloric acid, and illumination 30 minutes, obtain under sunlight HxWO3/ CdS compound (0 < x < 1)；Gained compound is added drop-wise in 25% nitric acid solution, stirring 1h clears up CdS sufficiently, It is 12 hours dry at 60 DEG C after washed again, obtain pure HxWO3Sample.
Embodiment 2
Weigh 300mg WCl6, be added 50mL dehydrated alcohol in, in 200 DEG C insulation reaction 10 hours, through ethyl alcohol and washing It is 12 hours dry at 60 DEG C after washing, obtain W18O49；Weigh gained W18O4940mg is scattered in 60mL H2In O, it is added 0.296g cadmium acetate and 0.06g thioacetamide, in 150 DEG C hydro-thermal insulation reaction 10 hours, obtain W18O49/CdS；Weigh institute Obtain W18O49/ CdS 500mg is added in the mixed solution of 45mL water and 5mL hydrochloric acid, and illumination 60 minutes, obtain under sunlight HxWO3/ CdS compound (0 < x < 1)；Gained compound is added drop-wise in 30% nitric acid solution, stirring 0.5h makes CdS sufficiently disappear Solution, then it is washed after dry 12 hours at 60 DEG C, obtain pure HxWO3Sample.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (3)

1. a kind of visible light catalytic assists the method for preparing pure hydrogen tungsten bronze, it is characterised in that: the following steps are included:
(1) with WCl6As predecessor, dehydrated alcohol is solvent, obtains W through solvent thermal reaction18O49；
(2) by gained W18O49It is dispersed in water, and cadmium acetate and thioacetamide is added, obtain W through hydro-thermal reaction18O49/CdS；
(3) by gained W18O49/ CdS is added in aqueous hydrochloric acid solution, obtains H through illuminationxWO3/ CdS compound, 0 < x < 1；
(4) by gained HxWO3/ CdS compound is added drop-wise in the nitric acid solution of low concentration, and stirring 1h clears up CdS sufficiently, then passes through Pure H is made in washing, dryingxWO3；
The volumetric concentration of aqueous hydrochloric acid solution described in step (3) is 5-10%；The illumination is shone under sunlight or artificial light source Penetrate 0.5-3h；
The volumetric concentration of nitric acid solution described in step (4) is 25-35%.
2. preparation method according to claim 1, it is characterised in that: the temperature of solvent thermal reaction described in step (1) is 100-200 DEG C, time 20-40h.
3. preparation method according to claim 1, it is characterised in that: the cadmium acetate and thioacetyl being added in step (2) The molar ratio of amine is 1.6:1；
The temperature of the hydro-thermal reaction is 100-200 DEG C, time 10-30h；
Gained W18O49W in/CdS18O49Mass ratio with CdS is 1:1-1:15.
CN201810049772.2A 2018-01-18 2018-01-18 A kind of method that visible light auxiliary prepares pure hydrogen tungsten bronze Expired - Fee Related CN107973346B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719891A (en) * 2011-06-14 2012-10-10 中国科学院金属研究所 Method for preparing tungsten trioxide crystals with controllable growth of crystal surfaces
CN105036196A (en) * 2015-08-27 2015-11-11 陕西科技大学 Preparation method of multi-dimensional pure-phase W18O49
CN106830085A (en) * 2017-01-24 2017-06-13 南昌大学 A kind of preparation method of stabilization hydrogen tungsten bronze nanometer sheet

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719891A (en) * 2011-06-14 2012-10-10 中国科学院金属研究所 Method for preparing tungsten trioxide crystals with controllable growth of crystal surfaces
CN105036196A (en) * 2015-08-27 2015-11-11 陕西科技大学 Preparation method of multi-dimensional pure-phase W18O49
CN106830085A (en) * 2017-01-24 2017-06-13 南昌大学 A kind of preparation method of stabilization hydrogen tungsten bronze nanometer sheet

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Direct Z-scheme composite of CdS and oxygen-defected CdWO4: Anefficient visible-light-driven photocatalyst for hydrogen evolution;Xu Jia et al.;《 Applied Catalysis B: Environmental》;20160521;第198卷;第154-161页 *
Variable barrier height semiconductor/HxWO3 diodes;R. D. Rauh et al.;《Applied Physics Letters》;19860203;第48卷(第5期);第362-364页 *

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