CN105214639A - A kind of Mg-Ce-ZrO 2the preparation method of catalysis material - Google Patents

Abstract

A kind of Mg-Ce-ZrO ₂the preparation method of catalysis material, relates to novel nano catalysis material technical field.Take ZrOCl ₂8H ₂o, C ₁₉h ₄₂brN, MgCl ₂6H ₂o and Ce (SO ₄) ₂4H ₂o puts into beaker; Weak aqua ammonia is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia until the pH value of solution is about 8; Encase beaker with preservative film, stir two hours; Solution is poured in reactor, be placed in baking oven and carry out hydro-thermal reaction; Suction filtration after product absolute ethanol washing, cyclic washing; Product is placed in crucible, again puts into baking oven dry; The product mortar porphyrize taken out, obtains Mg-Ce-ZrO ₂catalysis material, has the advantages such as photocatalytic activity is high, Heat stability is good, powder dispersibility are high, particle compactness is good, particle size distribution is even, perfection can be applied to catalysis material field.

Description

A kind of Mg-Ce-ZrO 2the preparation method of catalysis material

Technical field

The present invention relates to novel nano catalysis material technical field, specifically relate to a kind of Mg-Ce-ZrO ₂the preparation method of catalysis material.

Background technology

Material is the material base that the mankind depend on for existence and development, plays a very important role in national economy and social development.Along with electronics and new material industry are just at development, nanometer ZrO ₂and its composite will be widely used, be particularly applied to catalysis material technical field, research boom definitely will certainly be caused.

Zirconium dioxide (ZrO ₂) be an important function and structural material in modern industry and Material Field, it has very excellent physics and chemistry character, and hardness is inferior to diamond.Pure ZrO ₂be a kind of crystal of colorless and odorless, be insoluble in water, hydrochloric acid and dilute sulfuric acid, its chemical property torpescence, fusing point is high, hardness is large, resistivity and refractive index also all higher, and there is low thermal coefficient of expansion.But because its forbidden band is very wide, photocatalytic activity and heat endurance is lower, powder dispersibility is poor, therefore, it well cannot adapt to the requirement of catalysis material.

Chinese patent CN104475095A zirconium dioxide photochemical catalyst disclosing a kind of Ag doping and preparation method thereof, by to doping metals silver element in zirconium dioxide, to change the energy gap of zirconium dioxide, make it there is response at visible region, to improve the activity of zirconium dioxide.First preparation method calcines zirconium dioxide, then instills the aqueous solution of silver ion, is then prepared by hydro-thermal reaction.But this preparation method compares when Separation of Solid and Liquid and washing and is difficult to process, easily causes secondary pollution.The product obtained easily is reunited, and is not easy to be separated, and product powder dispersibility is poor, therefore needs when being applied to industrial production to add dispersant or surfactant.The reactor that this preparation method uses simultaneously is also very easy to be corroded.

Summary of the invention

In order to overcome the above-mentioned defect existed in prior art, an object of the present invention there are provided a kind of Mg-Ce-ZrO ₂the preparation method of catalysis material, the catalysis material that photocatalytic activity is high to prepare, Heat stability is good, powder dispersibility are high.

For realizing this object, present invention employs following technical scheme: a kind of Mg-Ce-ZrO ₂the preparation method of catalysis material, step is as follows:

1. the ZrOCl of 9.6675g, is taken ₂8H ₂the C of O, 1.0000g ₁₉h ₄₂the MgCl of BrN, 0.5367g ₂6H ₂ce (the SO of O and 1.0674g ₄) ₂4H ₂o puts into beaker;

2., measure 2.5mL concentrated ammonia liquor, adding distil water is diluted to 100mL, and the ammoniacal liquor after taking-up 50mL is diluted is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia while stirring with glass bar, until the pH value of solution stops dripping 7.5 ~ 8.5 time;

3., by magneton put into beaker, encase beaker with preservative film, prevent solution from exposing for a long time oxidized in atmosphere, by magnetic stirrer two hours;

4., by the solution after stirred pour in reactor, then be placed in baking oven by reactor, temperature is set to 80 DEG C, carries out hydro-thermal reaction, takes out after 24 hours;

5., after the cooling of the temperature of question response still, take out product, with after absolute ethanol washing with the multiplex vavuum pump suction filtration of circulating water type, cyclic washing suction filtration 3 times;

6., be placed in crucible by the product that suction filtration is good, again put into baking oven, temperature is still set to 80 DEG C, takes out after 24 hours;

7., the product mortar porphyrize that takes out, obtain end product---Mg-Ce-ZrO ₂catalysis material.

Compared with prior art, beneficial effect of the present invention shows:

Can be found out by SEM figure be doped with Mg and Ti and Ce, Mg and Ti, the carrier surface of Mg and Ce and Ti and Ce is made up of numerous fine particles, there is abundanter surface texture, prove thus, the element of doping is more, grain surface is long-pending larger, and doped metallic elements effectively avoids the reunion of particle.Mg-Ce-ZrO simultaneously ₂catalysis material also has the advantages such as photocatalytic activity is high, Heat stability is good, powder dispersibility are high, particle compactness is good, particle size distribution is even, perfection can be applied to catalysis material field.

Accompanying drawing explanation

Fig. 1 is the electron scanning micrograph of target product prepared by embodiment 1 ~ 4.

Target product prepared by Fig. 2 embodiment 1 and pure ZrO ₂infrared spectrogram.

The infrared spectrogram of target product prepared by Fig. 3 embodiment 2 ~ 4.

Fig. 4 is the target product of embodiment 1 ~ 4 preparation and pure ZrO ₂x-ray diffracting spectrum.

Fig. 5 is the thermogravimetric analysis figure of target product prepared by embodiment 1.

Fig. 6 is the size distribution curve of target product prepared by embodiment 1 ~ 4.

Fig. 7 is the target product of embodiment 1,4 preparation and pure ZrO ₂photocatalytic degradation experiment degradation rate--time graph.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is described in further detail.

Embodiment 1

Mg-Ti-Ce-ZrO ₂the preparation of catalysis material:

1. the ZrOCl of 9.6675g, is taken ₂8H ₂the C of O, 1.0000g ₁₉h ₄₂the MgCl of BrN, 0.3578g ₂6H ₂the TiCl of O, 0.2715g ₃with the Ce (SO of 0.7116g ₄) ₂4H ₂o puts into beaker.

2., measure 2.5mL concentrated ammonia liquor, adding distil water is diluted to 100mL, and the ammoniacal liquor after taking-up 50mL is diluted is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia while stirring with glass bar, until the pH value of solution stops dripping about 8 time.

3., by magneton put into beaker, encase beaker with preservative film, prevent solution from exposing for a long time oxidized in atmosphere, by magnetic stirrer two hours.

4., by the solution after stirred pour in reactor, then be placed in baking oven by reactor, temperature is set to 80 DEG C, carries out hydro-thermal reaction, takes out after 24 hours.

5., after the cooling of the temperature of question response still, take out product, with after absolute ethanol washing with the multiplex vavuum pump suction filtration of circulating water type, cyclic washing suction filtration 3 times.

6., be placed in crucible by the product that suction filtration is good, again put into baking oven, temperature is still set to 80 DEG C, takes out after 24 hours.

7., the product mortar porphyrize that takes out, obtain end product---Mg-Ti-Ce-ZrO ₂catalysis material.

Embodiment 2

Mg-Ti-ZrO ₂the preparation of catalysis material:

1. the ZrOCl of 9.6675g, is taken ₂8H ₂the C of O, 1.0000g ₁₉h ₄₂the MgCl of BrN, 0.5367g ₂6H ₂the TiCl of O and 0.4072g ₃put into beaker.

2., measure 2.5mL concentrated ammonia liquor, adding distil water is diluted to 100mL, and the ammoniacal liquor after taking-up 50mL is diluted is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia while stirring with glass bar, until the pH value of solution stops dripping about 8 time.

3., by magneton put into beaker, encase beaker with preservative film, prevent solution from exposing for a long time oxidized in atmosphere, by magnetic stirrer two hours.

4., by the solution after stirred pour in reactor, then be placed in baking oven by reactor, temperature is set to 80 DEG C, carries out hydro-thermal reaction, takes out after 24 hours.

5., after the cooling of the temperature of question response still, take out product, with after absolute ethanol washing with the multiplex vavuum pump suction filtration of circulating water type, cyclic washing suction filtration 3 times.

6., be placed in crucible by the product that suction filtration is good, again put into baking oven, temperature is still set to 80 DEG C, takes out after 24 hours.

7., the product mortar porphyrize that takes out, obtain end product---Mg-Ti-ZrO ₂catalysis material.

Embodiment 3

Mg-Ce-ZrO ₂the preparation of catalysis material:

1. the ZrOCl of 9.6675g, is taken ₂8H ₂the C of O, 1.0000g ₁₉h ₄₂the MgCl of BrN, 0.5367g ₂6H ₂ce (the SO of O and 1.0674g ₄) ₂4H ₂o puts into beaker.

2., measure 2.5mL concentrated ammonia liquor, adding distil water is diluted to 100mL, and the ammoniacal liquor after taking-up 50mL is diluted is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia while stirring with glass bar, until the pH value of solution stops dripping about 8 time.

3., by magneton put into beaker, encase beaker with preservative film, prevent solution from exposing for a long time oxidized in atmosphere, by magnetic stirrer two hours.

4., by the solution after stirred pour in reactor, then be placed in baking oven by reactor, temperature is set to 80 DEG C, carries out hydro-thermal reaction, takes out after 24 hours.

5., after the cooling of the temperature of question response still, take out product, with after absolute ethanol washing with the multiplex vavuum pump suction filtration of circulating water type, cyclic washing suction filtration 3 times.

6., be placed in crucible by the product that suction filtration is good, again put into baking oven, temperature is still set to 80 DEG C, takes out after 24 hours.

7., the product mortar porphyrize that takes out, obtain end product---Mg-Ce-ZrO ₂catalysis material.

Embodiment 4

Ti-Ce-ZrO ₂the preparation of catalysis material:

1. the ZrOCl of 9.6675g, is taken ₂8H ₂the C of O, 1.0000g ₁₉h ₄₂the TiCl of BrN, 0.4072g ₃with the Ce (SO of 1.0674g ₄) ₂4H ₂o puts into beaker.

2., measure 2.5mL concentrated ammonia liquor, adding distil water is diluted to 100mL, and the ammoniacal liquor after taking-up 50mL is diluted is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia while stirring with glass bar, until the pH value of solution stops dripping about 8 time.

3., by magneton put into beaker, encase beaker with preservative film, prevent solution from exposing for a long time oxidized in atmosphere, by magnetic stirrer two hours.

4., by the solution after stirred pour in reactor, then be placed in baking oven by reactor, temperature is set to 80 DEG C, carries out hydro-thermal reaction, takes out after 24 hours.

5., after the cooling of the temperature of question response still, take out product, with after absolute ethanol washing with the multiplex vavuum pump suction filtration of circulating water type, cyclic washing suction filtration 3 times.

6., be placed in crucible by the product that suction filtration is good, again put into baking oven, temperature is still set to 80 DEG C, takes out after 24 hours.

7., the product mortar porphyrize that takes out, obtain end product---Ti-Ce-ZrO ₂catalysis material.

Field emission scanning electron microscope (MG-SEM), fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), thermogravimetric differential thermal measuring instrument (TG/DSC) and Particle Size Analyzer (granulometer) is selected to characterize parameters such as its structure, pattern and compositions respectively to target product prepared by embodiment 1 ~ 4 below.

Fig. 1 a ~ Fig. 1 d is the electron scanning micrograph of target product prepared by embodiment 1 ~ 4 successively, be doped with Mg and Ti and Ce, Mg and Ti as seen in Figure 1 respectively, the carrier surface of Mg and Ce and Ti and Ce is made up of numerous fine particles, there is abundanter surface texture, prove thus, the element of doping is more, grain surface is long-pending larger, and doped metallic elements effectively avoids the reunion of particle.

A ~ e in Fig. 2 and 3 is target product, pure ZrO prepared by embodiment 1 ~ 4 successively ₂infrared spectrogram, can at 3410cm by Fig. 2 ^-1, 1320cm ^-1, 1620cm ^-1, 840cm ^-1, 800cm ^-1there is obvious characteristic absworption peak in place.Wherein in above absworption peak, the most roomy place is at 3410cm ^-1place, consult infrared absorption spectroscopy known is the contraction vibration peak of O-H herein.At 1320cm ^-1, 1620cm ^-1the absworption peak at place is because the symmetrical stretching vibration peak of hydroxyl, at 400cm ^-1to 900cm ^-1near wave number, peak is then because the stretching vibration peak of Zr-O and Ce-O key.

As seen from Figure 2, attend by a little rising of temperature in sintering process, originally comparatively sharp-pointed diffraction maximum rapidly disappears, originally comparatively roomy diffraction maximum, and narrow disappearance gradually, and whole collection of illustrative plates trend is level and smooth.When sample is heated to 700 DEG C, vanish from sight all substantially in previously mentioned all infrared ray diffraction peaks.The impurity such as moisture, nitrate and organic matter contained in interpret sample volatilize completely or decompose, and the reaction of whole crystalline formation all completes.Only surplus absworption peak can be summed up as M-O, and (wherein M is Ti ³⁺, Mg ²⁺, Ce ⁴⁺) characteristic peak of stretching vibration, illustrate that powder through 700 DEG C of sintering 2h is completely without dephasign existence, Ti ³⁺, Mg ²⁺, Ce ⁴⁺enter in zirconia skeleton or be at least compounded in zirconic surface.

In Fig. 4, a ~ e curve is target product, pure ZrO prepared by embodiment 1 ~ 4 successively ₂x-ray diffracting spectrum, each component has a stronger peak at about 33 ° as seen in Figure 4, this peak is generally the characteristic peak of Tetragonal zirconium, does not see the characteristic peak of Mg, Ti and Ce, is because these elements are well dispersed in zirconium dioxide.

Fig. 5 is the thermogravimetric analysis figure of target product prepared by embodiment 1, as seen in Figure 5 along with the rising of temperature, the weight of sample is reducing gradually, preliminary stage TG curve decrease speed is very fast, and in the comparatively steep mainly sample of the gradient, the crystallization water raises with temperature and the decomposition of impurity in evaporation and sample causes example weight sharply to decline.

200 DEG C of later zero-g periods mainly cause because violent redox occurs for the organic matter in sample, nitrate or metallic, organic substance decomposing in this process is described, combustion reaction occurs, intermediate product cracking and volatilizing with gaseous products, through the generation of this process, Mg, Ti, Ce ion enters ZrO substantially ₂lattice in the middle of.ZrO ₂crystal structure change.After 400 DEG C, curve is gradually mild, and interpret sample weight does not have too large change yet, tends towards stability, and basic maintenance former ponderable 75% illustrates that reaction completes, and sample structure is shaped, illustrates that each metallic element all enters zirconia skeleton with oxide.

Fig. 6 a ~ Fig. 6 d is the size distribution curve of target product prepared by embodiment 1 ~ 4 successively, it can thus be appreciated that after doping different component granularity generally distribute evenly a little and scope is narrower, the pure ZrO of ratio that wherein after doped with Mg-Ti-Ce, the granularity of particle becomes ₂less, but intensity is more weak, and the pure ZrO of strength ratio after doped with Mg-Ti, Mg-Ce ₂stronger, independent doped with Mg-Ti is described, Mg-Ce makes particle intensity stronger than doped with Mg-Ti-Ce.

Photocatalysis is tested

First the methyl orange solution preparing 20mg/L is placed in volumetric flask for subsequent use, measures with beaker the methyl orange solution that 60mL configures, and takes target product and pure ZrO prepared by 2mg embodiment 1,4 ₂sample, pours into sample in solution, ultrasonic and stir 30min under dark surrounds, then get and put into centrifuge tube (altogether 15 samples) for 5 times, remainingly also put into other centrifuge tubes, as blank assay, lid covers, labelled, under ultraviolet irradiation lamp, carry out catalytic degradation.Lamp, according in process, takes out one, lucifuge in every 5 the insides respectively after 0.5h, 2h, 5h.After 10h, the sample and blank assay that carried out illumination are contrasted color, if color dies down, illustrate that the sample added has catalytic action to methyl orange, shade intensity of variation indicates the power of catalytic.

According to the absorbance that each time point records, calculate degradation rate ( wherein A ₀for the initial absorbance of institute's test sample product, A is the final absorbance of institute's test sample product), take time as abscissa, degradation rate is ordinate, draws.

Result as shown in Figure 7, it can thus be appreciated that Mg-Ti-Ce-ZrO ₂the catalytic effect of powder is best, under uviol lamp, reach more than 85% according to the degradation rate of methyl orange after 5h.And with Ti-Ce-ZrO ₂during for catalyst degradation methyl orange, degradation rate also has 70% nearly, and therefore, a series of catalysis materials prepared by the present invention all have photocatalysis effect, all effectively can improve photocatalysis performance (improve 70% compared to 20% of pure zirconia degraded).

Claims (1)

1. a Mg-Ce-ZrO ₂the preparation method of catalysis material, is characterized in that step is as follows:

1. the ZrOCl of 9.6675g, is taken ₂8H ₂the C of O, 1.0000g ₁₉h ₄₂the MgCl of BrN, 0.5367g ₂6H ₂ce (the SO of O and 1.0674g ₄) ₂4H ₂o puts into beaker;

2., measure 2.5mL concentrated ammonia liquor, adding distil water is diluted to 100mL, and the ammoniacal liquor after taking-up 50mL is diluted is poured in beaker, and drips several absolute ethyl alcohols, drips weak aqua ammonia while stirring with glass bar, until the pH value of solution stops dripping 7.5 ~ 8.5 time;

3., by magneton put into beaker, encase beaker with preservative film, prevent solution from exposing for a long time oxidized in atmosphere, by magnetic stirrer two hours;

4., by the solution after stirred pour in reactor, then be placed in baking oven by reactor, temperature is set to 80 DEG C, carries out hydro-thermal reaction, takes out after 24 hours;

5., after the cooling of the temperature of question response still, take out product, with after absolute ethanol washing with the multiplex vavuum pump suction filtration of circulating water type, cyclic washing suction filtration 3 times;

6., be placed in crucible by the product that suction filtration is good, again put into baking oven, temperature is still set to 80 DEG C, takes out after 24 hours;

7., the product mortar porphyrize that takes out, obtain end product---Mg-Ce-ZrO ₂catalysis material.