CN106311211B

CN106311211B - The application of germanic acid zirconium

Info

Publication number: CN106311211B
Application number: CN201610850317.3A
Authority: CN
Inventors: 汤建庭; 李佳胤; 马新平
Original assignee: Hunan University of Science and Technology
Current assignee: Hunan University of Science and Technology
Priority date: 2016-09-26
Filing date: 2016-09-26
Publication date: 2018-08-28
Anticipated expiration: 2036-09-26
Also published as: CN106311211A

Abstract

The invention discloses a kind of germanic acid zirconium (ZrGeO₄) application, the application example of this compound is provided for the first time.ZrGeO₄As catalyst, even if can the organic dye pollutants such as rhodamine B degradation (RhB) and methylene blue (MB) if being protected from light under room temperature completely.In degradation experiment, ZrGeO₄It reuses three times, activity does not reduce, and continues to be repeated as many times, and activity also can preferably be kept, and declines without apparent.The ZrGeO of the present invention₄Do not depend on illumination, at ambient temperature can catalytic degradation organic dyestuff, durability it is high, be conducive to promote and apply.

Description

The application of germanic acid zirconium

Technical field

The invention belongs to technical field of environment pollution control, are related to germanic acid zirconium (ZrGeO₄) exist as a kind of new catalyst Application in degradating organic dye pollutant.

Background technology

With the increase of population, global printing and dyeing industry size constantly expands, a large amount of organic dyestuff of industry discharge Pollutant, it has also become the important sources of whole world water pollution.Photocatalitic Technique of Semiconductor can directly utilize sunlight at room temperature By dyestuff contaminant efficiently oxidative degradation.Therefore, by photocatalysis technology, sunlight is made full use of to carry out degradation of dye pollutant It is a beneficial way of Enviromental Pollution Treatment.Because ultraviolet light only accounts for 4% or so of sunshine gross energy, and visible light accounts for 46% or so, so being to utilize the visible light in sunlight using the key of solar energy.Therefore, it is seen that the light of photoresponse type is urged Agent is with important application prospects in current field of environmental improvement.However, because of the limitation of band structure, high light is added Raw Carrier recombination rate, it is seen that the activity and durability of photocatalyst for degrading dyestuff contaminant are generally relatively low.

Another beneficial way of degradation of dye pollutant is not by illumination, energy-efficient under room temperature using catalysis Agent carries out catalytic degradation.Develop high activity, high durability catalyst for no light, dyestuff contaminant under room temperature Degradation has important practical prospect and learning value in field of environment pollution control.

Many catalyst can show catalytic activity or even high activity under conditions of having illumination, but this active Obtain, usually to this condition of illumination highly dependent upon.If intensity of illumination is very weak, or does not have illumination, then can not show to urge Change activity, or even require just show activity for the irradiation of special wavelength light, this makes the application of catalyst be restricted. Therefore, research and development require lower catalyst to external condition, have broadening application range and reduce the important of application cost Meaning.

ZrGeO₄It is a kind of inorganic compound, although its preparation method and composition identification are already it has been reported that mesh It is preceding that there has been no patents and document report ZrGeO₄Application study, especially its application study as catalyst.

Invention content

Present invention aims at provide germanic acid zirconium (ZrGeO₄) in a kind of new opplication of field of environmental improvement, this is provided for the first time The application example of compound.

The technical scheme is that：

A kind of application of germanic acid zirconium, ZrGeO₄As catalyst degradation organic dye pollutant, the step of concrete application, is：

(1) using organic dye pollutant as substrate, with ZrGeO₄Catalytic degradation is carried out for catalyst；

(2)ZrGeO₄The activity rating of catalyst：The degradation rate for measuring organic dye pollutant, with its degradable institute The time needed weighs its catalytic activity.

The application of above-mentioned germanic acid zirconium, the organic dye pollutant are preferably rhodamine B (RhB) or methylene blue (MB), the catalytic degradation, temperature are 10~25 DEG C, and illumination condition is to be protected from light completely or natural light irradiation.

The beneficial effects of the present invention are：

(1) the experimental results showed that, ZrGeO₄Even if be protected from light completely under room temperature can effectively rhodamine B degradation or The organic dyestuff such as methylene blue.In degradation experiment, ZrGeO₄It reuses three times, activity does not reduce；Continue to reuse Repeatedly, activity still declines without apparent, shows very high durability.

(2) ZrGeO of the invention₄Illumination condition is needed not rely on when catalytic degradation dyestuff, to temperature also almost without wanting It asks, durability height, there is good application value.

Description of the drawings

Fig. 1 is ZrGeO prepared by the embodiment of the present invention 1₄The XRD diagram of catalyst.

Fig. 2 is ZrGeO prepared by the embodiment of the present invention 1₄The Activity Results and ZrGeO of degradation RhB dyestuffs₄It reuses Activity Results.Wherein, C₀The initial concentration of RhB before being added for catalyst, C be in catalytic process under any moment RhB it is dense Degree.

Fig. 3 is ZrGeO prepared by the embodiment of the present invention 1₄The Activity Results and ZrGeO of degradation MB dyestuffs₄It reuses Activity Results.Wherein, C₀The initial concentration of MB before being added for catalyst, the concentration that C is MB under any moment in catalytic process.

Specific implementation mode

Here is ZrGeO of the present invention₄With the specific embodiment of application study, following embodiment is further intended to be described in detail The present invention is not intended to limit the present invention.

Embodiment 1

(1)ZrGeO₄Preparation

Take the ZrOCl of 20mmol₂It is dissolved in 100ml deionized waters, then adds the GeO of 20mmol₂, at room temperature Stirring 30 minutes.Gained mixture is transferred in the autoclave that volume is 150mL, it is natural after being stood for 24 hours at 220 DEG C It is cooled to room temperature.Gained precipitation is washed with deionized and (uses deionized water 50mL every time) three times, after centrifugation, is placed in temperature The oven drying that degree is 60 DEG C is for 24 hours.Finally, by obtained solid at 900 DEG C calcination 2 hours up to ZrGeO₄Sample.

(2)ZrGeO₄Characterization

From the XRD diagram of Fig. 1 as it can be seen that ZrGeO₄The crystalline phase of sample with《Powder diffraction card set》Middle JCPDS No.34-0407 Standard ZrGeO₄Crystalline phase fits like a glove, this illustrates ZrGeO₄Sample is successfully prepared.

(3)ZrGeO₄The active testing of catalytic degradation RhB

By the ZrGeO of 150mg₄The RhB solution that catalyst is placed in a concentration of 3mg/L of 100mL (is contained in the opening of 400mL Beaker) in, in the stirring at room temperature being protected from light completely.It samples in different time points respectively, supernatant is taken after centrifugation, by supernatant Liquid dilutes to obtain sample.It is measured with ultraviolet specrophotometer (general analysis TU1810, Beijing Puxi General Instrument Co., Ltd) Absorbance of the sample at 554nm.The RhB concentration of sample is finally calculated according to concentration-absorbance standard curve.

(4)ZrGeO₄The active testing of catalytic degradation MB

By the ZrGeO of 150mg₄The MB solution that catalyst is placed in a concentration of 6mg/L of 100mL (is contained in the open of 400mL to burn Cup) in, in the stirring at room temperature being protected from light completely.It samples in different time points respectively, supernatant is taken after centrifugation, by supernatant Dilution obtains sample.It is measured and is tried with ultraviolet specrophotometer (general analysis TU1810, Beijing Puxi General Instrument Co., Ltd) Absorbance of the sample at 665nm.The MB concentration of sample is finally calculated according to concentration-absorbance standard curve.

Activity experiment the result shows that, be protected from light completely under room temperature, ZrGeO₄Catalyst can contaminate RhB in 10h Expect degradable (Fig. 2), can degrade MB dyestuffs in 16h 75~80% (Fig. 3).In the degradation experiment of RhB and MB dyestuffs, ZrGeO₄It reuses three times, activity does not reduce.Continue to be reused many times in addition, experimental result is also shown that, activity remains to It preferably keeps, declines without apparent activity.Therefore, ZrGeO₄Catalyst degradation RhB or MB dyestuff is one energy saving, efficient Process has potential application prospect in terms of environmental pollution improvement.

Claims

1. a kind of application of germanic acid zirconium, which is characterized in that ZrGeO₄As catalyst degradation organic pollution, the step of concrete application Suddenly it is：

Using organic dye pollutant as substrate, with ZrGeO₄Catalytic degradation is carried out for catalyst, temperature is 10 ~ 25 DEG C, illumination condition To be protected from light completely or natural light irradiation；

The activity rating of catalyst：The degradation rate for measuring organic dye pollutant is weighed degradable required time with its Measure its catalytic activity；

The organic dye pollutant is rhodamine B or methylene blue.