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

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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
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China
Prior art keywords
rare earth
titanium dioxide
mixes
optical catalyst
boron nitrogen
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CN201510523135.0A
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Chinese (zh)
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于耀光
敖冬飞
陈刚
张相彬
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Harbin Institute of Technology
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Harbin Institute of Technology
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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)

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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

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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

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Application publication date: 20151223