CN105170171A - Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst - Google Patents

Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst Download PDF

Info

Publication number
CN105170171A
CN105170171A CN201510523135.0A CN201510523135A CN105170171A CN 105170171 A CN105170171 A CN 105170171A CN 201510523135 A CN201510523135 A CN 201510523135A CN 105170171 A CN105170171 A CN 105170171A
Authority
CN
China
Prior art keywords
rare earth
titanium dioxide
mixes
optical catalyst
boron nitrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510523135.0A
Other languages
Chinese (zh)
Inventor
于耀光
敖冬飞
陈刚
张相彬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201510523135.0A priority Critical patent/CN105170171A/en
Publication of CN105170171A publication Critical patent/CN105170171A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses a preparation method of a rare earth composite boron-nitrogen co-doped titanium dioxide catalyst, relates to a preparation method of a photocatalyst material, and belongs to the technical field of titanium dioxide photocatalyst. The invention aims to solve the problems that in the prior art, the cost is high, the energy consumption is huge, and the pollution is serious. The preparation method comprises the following steps: step one, preparing a rare earth salt solution; step two, preparing TiO2 suspension; step three, dispersing and drying through baking; step four, burning. The preparation method has the advantages of simple technology, convenient operation, low cost, little energy consumption, and no pollution. The prepared rare earth composite boron-nitrogen co-doped titanium dioxide catalyst has a good adsorption performance in visible light catalyzed reactions and high photocatalytic activity. The provided preparation method is used to prepare a rare earth composite boron-nitrogen co-doped titanium dioxide catalyst.

Description

A kind of rare earth compound boron nitrogen mixes the preparation method of titanium dioxide optical catalyst altogether
Technical field
The present invention relates to the preparation method of photocatalyst material, belong to titanium dioxide optical catalyst technical field.
Background technology
Along with the quickening of industrial process, a large amount of waste water, waste gas are discharged in rivers and air, and the toxic organics wherein contained can enrichment in human body, brings huge threat to human health.Solar energy photocatalytic process organic pollution technology becomes the focus of research gradually because of its efficient, inexpensive, nontoxic, energy-conservation advantage, and the research and development of corresponding light catalyst also become one of popular research field in the current world.
Through the effort of more than 40 years different field researchers, photocatalysis field has obtained deeply, research and development widely.TiO 2the features such as the photocatalysis performance superior with it and chemically-resistant, photochemical corrosion, nontoxic, cost is low become the focus paid close attention in photocatalysis field.But TiO 2energy gap is greater than 3.0eV, only can absorb account for whole solar spectrum less than 5% ultraviolet light, quantum yield is low, seriously limits its application in practice.Therefore the TiO of narrow band gap is prepared 2become the effective means fundamentally improving solar energy utilization ratio.
Summary of the invention
The present invention will solve existing method and prepare photochemical catalyst to there is cost high, and power consumption is large, pollutes heavy technical problem, and provides a kind of rare earth compound boron nitrogen to mix the preparation method of titanium dioxide optical catalyst altogether.
Rare earth compound boron nitrogen mixes a preparation method for titanium dioxide optical catalyst altogether, specifically carries out according to following steps:
One, rare earth oxide is dissolved in rare acid solution, adds the rare earth element salting liquid that distilled water compound concentration is 0.003 ~ 0.009mol/L;
Two, 0.05 ~ 0.1g boracic TiO is taken 2presoma, then adds the rare earth element salting liquid that step one obtains, and the compound quantity controlling rare earth element counts 1% ~ 5% by molar fraction, obtains TiO 2suspension;
Three, TiO step 2 obtained 2suspension ultrasonic disperse 20 ~ 40min, is then dry in 60 ~ 80 DEG C of baking ovens in temperature, obtains Powdered middle product;
Four, Powdered middle product grinding step 3 obtained, then puts into porcelain boat, in tube furnace, and NH 3carry out calcination under atmospheric condition, obtain a kind of rare earth compound boron nitrogen and mix titanium dioxide optical catalyst altogether.
Rare earth element has abundant energy level, special 4f electron transition characteristic and optical property, effectively can promote the performance of photochemical catalyst with the form of semiconductors coupling.Semiconductors coupling a kind ofly improves separation of charge efficiency, light stable catalyst and the effective means of expansion visible spectrum responses scope.Rare earth element, at semiconductor surface compound tense, can be formed " knot ", in the both sides of knot due to its can with etc. the difference of character can form space potential difference.This space potential difference have the separation being beneficial to electron-hole, light-catalysed efficiency can be improved.Meanwhile, owing to being mixed with boron and nitrogen, the energy gap of titanium dioxide being reduced greatly, improves light-catalysed efficiency.
The invention has the beneficial effects as follows: the inventive method is compared with additive method, adopt the method for solid-phase sintering to prepare rare earth compound boron nitrogen and mix titanium dioxide altogether, preparation technology is simple, simple operation, cost is low, consume energy little, pollution-free, and preparation rare earth compound boron nitrogen mix altogether titanium dioxide visible light photocatalysis reaction in there is good absorption property and photocatalytic activity.
The present invention mixes titanium dioxide optical catalyst altogether for the preparation of a kind of rare earth compound boron nitrogen.
Accompanying drawing explanation
Er compound boron nitrogen prepared by Fig. 1 embodiment one mixes the SEM photo of titanium dioxide optical catalyst altogether; Fig. 2 is XRD spectra; Fig. 3 is EDS spectrogram;
Er compound boron nitrogen prepared by Fig. 4 embodiment one mixes the UV-vis absorption spectra comparison diagram of titanium dioxide optical catalyst and P25 altogether, and wherein curve 1 represents photochemical catalyst prepared by the present embodiment, and curve 2 represents P25;
Fig. 5 is that Er compound boron nitrogen prepared by embodiment two mixes the SEM photo of titanium dioxide optical catalyst altogether.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: a kind of rare earth compound of present embodiment boron nitrogen mixes the preparation method of titanium dioxide optical catalyst altogether, specifically carries out according to following steps:
One, rare earth oxide is dissolved in rare acid solution, adds the rare earth element salting liquid that distilled water compound concentration is 0.003 ~ 0.009mol/L;
Two, 0.05 ~ 0.1g boracic TiO is taken 2presoma, then adds the rare earth element salting liquid that step one obtains, and the compound quantity controlling rare earth element counts 1% ~ 5% by molar fraction, obtains TiO 2suspension;
Three, TiO step 2 obtained 2suspension ultrasonic disperse 20 ~ 40min, is then dry in 60 ~ 80 DEG C of baking ovens in temperature, obtains Powdered middle product;
Four, Powdered middle product grinding step 3 obtained, then puts into porcelain boat, in tube furnace, and NH 3carry out calcination under atmospheric condition, obtain a kind of rare earth compound boron nitrogen and mix titanium dioxide optical catalyst altogether.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: step one middle rare earth is dysprosium oxide, Er oxide or thulium oxide.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike: acid solution rare described in step one is dilute hydrochloric acid solution, dilute nitric acid solution or dilution heat of sulfuric acid.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are unlike boracic TiO in step 2 2presoma is with TiB 2for raw material, be that in the hydrochloric acid solution of 0.2 ~ 0.8mol/L, hydrolysis is obtained in concentration, wherein, during hydrolysis, control temperature is 160 ~ 200 DEG C, and the reaction time is 24 ~ 48h.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: in step 4, calcination temperature is 600 ~ 1000 DEG C.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: in step 4, calcination temperature is 800 DEG C.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six unlike: in step 4, calcination time is 6 ~ 10h.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven unlike: grind 5min in step 4.Other is identical with one of detailed description of the invention one to seven.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
A kind of rare earth compound of the present embodiment boron nitrogen mixes the preparation method of titanium dioxide optical catalyst altogether, specifically carries out according to following steps:
One, by 0.3153gEr 2o 3be dissolved in watery hydrochloric acid, then adopt distilled water to be settled to 250mL, obtain rare earth element salting liquid;
Two, 0.05g boracic TiO is taken 2presoma, then adds the rare earth element salting liquid that 1.92mL step one obtains, obtains TiO 2suspension; Boracic TiO 2presoma is with TiB 2for raw material, be that in the hydrochloric acid solution of 0.5mol/L, hydrolysis is obtained in concentration, wherein, during hydrolysis, control temperature is 180 DEG C, and the reaction time is 24h;
Three, TiO step 2 obtained 2suspension ultrasonic disperse 30min, is then dry in 60 DEG C of baking ovens in temperature, obtains Powdered middle product;
Four, Powdered middle product grinding step 3 obtained, then puts into porcelain boat, in tube furnace, and NH 3under atmospheric condition, control temperature is 1000 DEG C, calcination 6h, obtains Er compound boron nitrogen and mixes titanium dioxide optical catalyst altogether.
Er compound boron nitrogen prepared by the present embodiment mixes the SEM photo of titanium dioxide optical catalyst as shown in Figure 1 altogether; XRD spectra as shown in Figure 2; EDS spectrogram as shown in Figure 3;
Er compound boron nitrogen prepared by the present embodiment mixes the UV-vis absorption spectra comparison diagram of titanium dioxide optical catalyst and P25 as shown in Figure 4 altogether, and wherein curve 1 represents photochemical catalyst prepared by the present embodiment, and curve 2 represents P25.
The method of this method employing solid-phase sintering is prepared rare earth compound boron nitrogen and is mixed titanium dioxide altogether, and preparation technology is simple, and simple operation, cost is low, consumes energy little, pollution-free.As can be seen from the figure the photochemical catalyst pattern that this law is obtained is homogeneous, and comparing with P25 all has raising by a relatively large margin at whole solar spectrum scope internal absorptance.
Embodiment two:
A kind of rare earth compound of the present embodiment boron nitrogen mixes the preparation method of titanium dioxide optical catalyst altogether, specifically carries out according to following steps:
One, by 0.3074gDy 2o 3be dissolved in dust technology, then adopt distilled water to be settled to 250mL, obtain rare earth element salting liquid;
Two, 0.10g boracic TiO is taken 2presoma, then adds the rare earth element salting liquid that 3.84mL step one obtains, obtains TiO 2suspension; Boracic TiO 2presoma is with TiB 2for raw material, be that in the hydrochloric acid solution of 0.5mol/L, hydrolysis is obtained in concentration, wherein, during hydrolysis, control temperature is 180 DEG C, and the reaction time is 24h;
Three, TiO step 2 obtained 2suspension ultrasonic disperse 30min, is then dry in 80 DEG C of baking ovens in temperature, obtains Powdered middle product;
Four, Powdered middle product grinding 5min step 3 obtained, then puts into porcelain boat, in tube furnace, and NH 3under atmospheric condition, control temperature is 800 DEG C, calcination 8h, obtains Dy compound boron nitrogen and mixes titanium dioxide optical catalyst altogether.
Er compound boron nitrogen prepared by the present embodiment mixes the SEM photo of titanium dioxide optical catalyst altogether as Fig. 5.

Claims (8)

1. rare earth compound boron nitrogen mixes a preparation method for titanium dioxide optical catalyst altogether, it is characterized in that what the method was specifically carried out according to following steps:
One, rare earth oxide is dissolved in rare acid solution, adds the rare earth element salting liquid that distilled water compound concentration is 0.003 ~ 0.009mol/L;
Two, 0.05 ~ 0.1g boracic TiO is taken 2presoma, then adds the rare earth element salting liquid that step one obtains, and the compound quantity controlling rare earth element counts 1% ~ 5% by molar fraction, obtains TiO 2suspension;
Three, TiO step 2 obtained 2suspension ultrasonic disperse 20 ~ 40min, is then dry in 60 ~ 80 DEG C of baking ovens in temperature, obtains Powdered middle product;
Four, Powdered middle product grinding step 3 obtained, then puts into porcelain boat, in tube furnace, and NH 3carry out calcination under atmospheric condition, obtain a kind of rare earth compound boron nitrogen and mix titanium dioxide optical catalyst altogether.
2. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that step one middle rare earth is dysprosium oxide, Er oxide or thulium oxide.
3. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that acid solution rare described in step one is dilute hydrochloric acid solution, dilute nitric acid solution or dilution heat of sulfuric acid.
4. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that boracic TiO in step 2 2presoma is with TiB 2for raw material, be that in the hydrochloric acid solution of 0.2 ~ 0.8mol/L, hydrolysis is obtained in concentration, wherein, during hydrolysis, control temperature is 160 ~ 200 DEG C, and the reaction time is 24 ~ 48h.
5. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that in step 4, calcination temperature is 600 ~ 1000 DEG C.
6. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that in step 4, calcination temperature is 800 DEG C.
7. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that in step 4, calcination time is 6 ~ 10h.
8. a kind of rare earth compound boron nitrogen according to claim 1 mixes the preparation method of titanium dioxide optical catalyst altogether, it is characterized in that grinding 5min in step 4.
CN201510523135.0A 2015-08-24 2015-08-24 Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst Pending CN105170171A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510523135.0A CN105170171A (en) 2015-08-24 2015-08-24 Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510523135.0A CN105170171A (en) 2015-08-24 2015-08-24 Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst

Publications (1)

Publication Number Publication Date
CN105170171A true CN105170171A (en) 2015-12-23

Family

ID=54892880

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510523135.0A Pending CN105170171A (en) 2015-08-24 2015-08-24 Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst

Country Status (1)

Country Link
CN (1) CN105170171A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106076307A (en) * 2016-06-06 2016-11-09 吕浩然 A kind of preparation method of rare earth element coblended nano TiO 2 photocatalyst
CN107894448A (en) * 2017-11-09 2018-04-10 福州大学 A kind of light of boron doped titanic oxide helps gas sensor and preparation method and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503930A2 (en) * 1991-03-13 1992-09-16 Advanced Ceramics Corporation Production of titanium diboride and boron nitride powders
CN1557540A (en) * 2004-02-13 2004-12-29 中国科学院上海硅酸盐研究所 Nitrogen doped titanium oxide mesoporous photocatalysis material and preparation method thereof
CN101327425A (en) * 2007-06-21 2008-12-24 河南大学 Method for preparing nitrogen-doped titanium dioxide photocatalyst
CN101596457A (en) * 2009-07-06 2009-12-09 宁波山泉建材有限公司 The nano titanium dioxide photocatalyst and the preparation method of boron and other element codope
CN104525236A (en) * 2014-12-24 2015-04-22 陕西科技大学 Process for preparing nanometer titanium dioxide ternary photocatalyst doped with nitrogen and rare earth elements
CN104607165A (en) * 2015-02-10 2015-05-13 哈尔滨工业大学 Preparation method of photocatalyst containing boron cross-shaped titanium dioxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503930A2 (en) * 1991-03-13 1992-09-16 Advanced Ceramics Corporation Production of titanium diboride and boron nitride powders
CN1557540A (en) * 2004-02-13 2004-12-29 中国科学院上海硅酸盐研究所 Nitrogen doped titanium oxide mesoporous photocatalysis material and preparation method thereof
CN101327425A (en) * 2007-06-21 2008-12-24 河南大学 Method for preparing nitrogen-doped titanium dioxide photocatalyst
CN101596457A (en) * 2009-07-06 2009-12-09 宁波山泉建材有限公司 The nano titanium dioxide photocatalyst and the preparation method of boron and other element codope
CN104525236A (en) * 2014-12-24 2015-04-22 陕西科技大学 Process for preparing nanometer titanium dioxide ternary photocatalyst doped with nitrogen and rare earth elements
CN104607165A (en) * 2015-02-10 2015-05-13 哈尔滨工业大学 Preparation method of photocatalyst containing boron cross-shaped titanium dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MANG NIU ET AL: "Understanding Photoelectrochemical Properties of B−N Codoped Anatase TiO2 for Solar Energy Conversion", 《THE JOUANAL OF PHYSICAL CHEMISTRY》 *
刘小珍: "《稀土精细化学品化学》", 31 July 2009, 化学工业出版社，第1版 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106076307A (en) * 2016-06-06 2016-11-09 吕浩然 A kind of preparation method of rare earth element coblended nano TiO 2 photocatalyst
CN106076307B (en) * 2016-06-06 2018-11-20 吕浩然 A kind of preparation method of rare earth element coblended nano TiO 2 photocatalyst
CN107894448A (en) * 2017-11-09 2018-04-10 福州大学 A kind of light of boron doped titanic oxide helps gas sensor and preparation method and application

Similar Documents

Publication Publication Date Title
CN105056981B (en) Preparation and application of composite photocatalyst g-C3N4-BiFeO3 for efficiently removing persistent organic pollutants
CN104128184A (en) Floating type CoFe2O4/TiO2/floating bead composite photocatalyst and preparation method thereof
CN104998672A (en) G-C3N4/{001}TiO2 composite visible-light-driven photocatalyst and preparation method and application thereof
CN102489324B (en) F and N co-doped visible-light response bismuth vanadate photocatalyst and preparation method thereof
CN101444724A (en) Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst
CN103191725B (en) BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof
CN105148949A (en) Bismuth oxyiodide-bismuth vanadium oxide heterojunction photocatalyst and preparation method thereof
CN105214689A (en) A kind of TiO 2/ CdS/ Graphene composite photocatalyst material and preparation method thereof
CN103240073B (en) Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof
CN105771958B (en) A kind of Bi4V2O11The preparation method of nano particle
CN105195133A (en) Preparation method of molybdenum disulfide-black titanium dioxide composite visible-light-driven photocatalyst for hydrogen production
CN105195198A (en) Mpg-C3N4/Bi0.9Nd0.1VO4 composite photocatalyst and preparation method and application thereof
CN106334554A (en) ZnO/Ag composite nano-photocatalyst with high-efficiency photocatalytic activity under visible lights
CN105772045B (en) A kind of BiPO4‑ZnFe2O4Composite photo-catalyst and preparation method thereof
CN108940332B (en) High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst
CN108889289A (en) A kind of titanium dioxide optical catalyst preparation and its application for receiving micron silicon Particles dispersed
CN106000390A (en) Method for preparation of Bi2O3/BiTaO4 composite photocatalyst by molten salt technique
CN104148099B (en) A kind of MoS2-BiPO4The preparation method of composite photo-catalyst
CN105170171A (en) Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst
CN103721713B (en) A kind of three-phase composite visible of efficient degradation dyestuff
CN105435827A (en) Preparation method for ternary-system TiO2/WS2/g-C3N4 composite photocatalyst with visible-light activity
CN107876039A (en) The preparation method of graphene cerium oxide hybrid material
CN104148093A (en) Preparation method for Bi2WO6-MoS2 composite photocatalyst
CN107352519B (en) A kind of C3N4The preparation method of nano wire
CN106268746A (en) A kind of high activity compound oxidizing zinc photocatalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20151223