A kind of renewable preparation method who recycles lithium fluoride modified titanic oxide nanocatalyst
Technical field
The present invention relates to a kind of renewable preparation method who recycles lithium fluoride modified titanic oxide nanocatalyst, be mainly used in sewage disposal and photocatalysis to degrade organic matter, belong to Photocatalitic Technique of Semiconductor and sewage purification field.
Background technology
Consume excessively and the environmental pollution of water resource causes shortage of water resources to become the matter of utmost importance of global concern.China's water resource area skewness weighing apparatus, water resource is relatively poor, and along with the continuous aggravation of water pollution, available water resource is very limited.Water pollution destroys ecological environment, is detrimental to health, and affects national economy, has greatly restricted the national economic development, and therefore, sewage disposal and purification are large problems that needs to be resolved hurrily at present.The two large principal elements that affects at present water quality are pathogenic microorganisms and poisonous chemicals in water, and wherein, what give prominence to the most is Organic Pollution in water body.Investigation shows, the river of China 80% left and right all is subject to Organic Pollution in various degree, and some organic pollutants is degraded slowly in environment, and the holdup time is long, can form directly threat to aquatic object and health by the enrichment conveying effect of biomagnification and food chain, produce potential hazard.Therefore, adopting the Organic Pollution in the method degradation of sewage of energy-efficient, environmental protection is a large focus of present sewage disposal.
At present, domestic dye wastewater treatment using, generally take bioanalysis as main, is aided with chemical method simultaneously, but decolouring and COD poor removal effect, water outlet is difficult to the stable discharge standard that reaches national regulation.Photocatalytic oxidation is one of focus of the research of water treatment in recent years, has the advantages such as energy consumption is low, easy and simple to handle, non-secondary pollution because of it, has caused researcher's extensive concern, is considered to the new type water treatment technology of environmental friendliness, sustainable development.Titanium dioxide, as a kind of multifunctional semiconductor material, has the function of photochemical catalytic oxidation wastewater organic pollutant, has active high, good stability,, low cost and other advantages nontoxic to human body, and potentiality are huge aspect sewage disposal
Become the study hotspot of present photocatalyst material greatly.Yet due to pure titinium dioxide belong to wide bandgap semiconductor (3.0~3.2eV), can only absorb ultraviolet light, cause catalytic efficiency lower.For this reason, people adopt several different methods to carry out modification to titanium dioxide, make it the more effective sunshine that utilizes, and, to improve titanium dioxide to organic disposal ability, reach the level of business application.Ion doping or modification are ways comparatively commonly used at present.By the doping vario-property to titanium dioxide, can effectively improve the photoresponse in the visible-range class, greatly improve its degradation capability.But all there is " poisoning " problem in present most catalyst, and the use of can't regenerating, be unfavorable for cost.
Summary of the invention
The objective of the invention is for existing issue, propose a kind of preparation method of the renewable lithium fluoride modified titanic oxide nanocatalyst that recycles.By hydro-thermal method lithium fluoride decorated nanometer titanium dioxide granule, greatly strengthen the adsorption effect of titanium dioxide to organic dyestuff, strengthen the photo-catalysis capability of titanium dioxide, make it at visible light wave range, good degradation effect be arranged also.
Second purpose of the present invention is the renovation process that proposes above-mentioned catalyst.
The renewable lithium fluoride modified titanic oxide nanocatalyst that recycles that the present invention proposes adopts secondary hydro-thermal legal system standby, and its concrete preparation method is as follows:
1), prepare titanic oxide nano powder
A), the configuration precursor solution, its component is: be 98% dense H with concentration
2SO
4The HCl mol ratio that is 37% with concentration is 3:4, adds deionized water, makes the H of solution
+Concentration remains on 0.1mol/L, and adding concentration is that 98% butyl titanate 1-15ml mixes;
B), sulfuric acid, hydrochloric acid and water are stirred after, drip butyl titanate and fully stir, the precursor solution that stirs is poured in reactor into 80 ~ 160 ℃ of hydro-thermal reaction 10 ~ 20h;
C), after the question response still naturally cools to room temperature, sample is taken out, clean powder to neutral.Oven dry, grind, and namely obtains titanic oxide nano powder;
2), the preparation of lithium fluoride modified titanic oxide nanometer powder
Add in the mixed solution of ethanol and water concentration of alcohol percent by volume 10-90%, uniform stirring, 120-180 ℃ of hydro-thermal reaction 10-20h with analyzing the titanic oxide nano powder that pure lithium fluoride and upper step make;
After the question response still naturally cools to room temperature, sample is taken out, oven dry, grind; 400-600 ℃ of annealing 1-3h, can obtain lithium fluoride modified titanic oxide nanocatalyst powder sample.
In the preparation of the nano titanium oxide nanocatalyst that above-mentioned lithium fluoride is modified, the molar ratio range of Li and Ti element is 0.25 ~ 1:1.
Following material can be adopted in the titanium source in the titanic oxide nano powder preparation: butyl titanate, isopropyl titanate, titanium sulfate.
The powder that adopts said method to make is the mixture (accompanying drawing 1) that lithium fluoride and anatase phase titanium dioxide coexist, and average particle size particle size is 20 ~ 30nm(accompanying drawing 2).Can reach 92% to organic adsorption rate in ultrasonic 10 minutes, the visible light photocatalytic degradation rate can reach 60%.
, through 400-600 ℃ of annealing heat treatment 1 ~ 3 hour, after making the organic matter volatilization, can again be used for absorption and photocatalytic degradation to organic pollution to the powder after absorption.And independent anatase phase titanium dioxide and lithium fluoride all do not have this effect.As everyone knows, the catalytic effect of anatase titania will be higher than red schorl phase titanium dioxide, after adopting lithium fluoride to modify, the F ion can suppress the transformation of titanium dioxide from anatase to Rutile Type, and Li ion atoms radius (0.76) is smaller, easily enters the titanium dioxide interstitial void, improves the ability of titanium dioxide surface absorption hydroxyl radical free radical OH, oxidative decomposition capacity is stronger, thereby greatly is beneficial to absorption and the photocatalytic degradation efficiency that improves titanium dioxide.
The catalyst of the method preparation has strong adsorption effect to organic matter, degradation of organic substances under visible light, renewable recycling also after annealing in process, can be widely used in the fields such as sewage disposal, photocatalysis organic matter degradation, the preparation method is simple and efficient, pollution-free, and reproducible utilization, greatly reduce and produce and use cost.
Description of drawings
Accompanying drawing 1 is the XRD collection of illustrative plates of the titania powder of lithium fluoride modification.Show sample is anatase as a result
The mixture of titanium dioxide and lithium fluoride.
Accompanying drawing 2 is TEM figure of the titania powder of lithium fluoride modification.The show sample average particle size particle size is 20 ~ 30nm.
The specific embodiment
Below the present invention is further described with embodiment.
Case study on implementation 1
The precursor solution for preparing titanic oxide nano powder is: deionized water 135ml, and concentration is 98% sulfuric acid 2.4ml, and concentration is 37% hydrochloric acid 1.85ml, and concentration is 98% butyl titanate 10ml.Dropwise add butyl titanate after acid and water are fully mixed, by magnetic agitation and fully mix, obtain faint yellow settled solution.Then solution is poured in reactor, put into 80 ℃ of hydro-thermal reactions of drying box after sealing 10 hours.To react the sediment that generates after the question response still is cooling and pour out, and with deionized water, repeatedly rinse to neutrality, oven dry obtains the anatase phase titanium dioxide nanometer powder after grinding.
Lithium fluoride powder and the anatase-phase nano titanium dioxide that makes are added the mixed solution of 20ml deionized water and 30ml alcohol by the mol ratio of Li:Ti=0.5:1, pour reactor into after fully stirring, 120 ℃ were reacted 12 hours.Oven dry is annealed 400 ℃ after grinding, and namely obtains the titanium dioxide nano photocatalysis agent that lithium fluoride is modified.
The sample of getting the 0.1g modified joins in the methylene blue solution that 50ml concentration is 4mg/L, and ultrasonic processing is 10 minutes under dark surrounds, carries out testing adsorption effect.The result demonstration, adsorption efficiency was 92% in ultrasonic 10 minutes.
To adsorb 400 ℃ of lower annealing in process of sample 2 hours of methylene blue, catalytic degradation methylene blue solution under visible light, degradation rate can reach 51% in 4 hours.
Case study on implementation 2
The precursor solution for preparing titanic oxide nano powder is: deionized water 135ml, and concentration is 98% sulfuric acid 2.4ml, and concentration is 37% hydrochloric acid 1.85ml, and concentration is 98% butyl titanate 10ml.Dropwise add butyl titanate after acid and water are fully mixed, by magnetic agitation, fully mix, obtain faint yellow settled solution.Then solution is poured in reactor, put into 80 ℃ of hydro-thermal reactions of drying box after sealing 10 hours.To react the sediment that generates after the question response still is cooling and pour out, and with deionized water, repeatedly rinse to neutrality, oven dry obtains the anatase phase titanium dioxide nanometer powder after grinding.
The mixed solution that lithium fluoride powder and the mol ratio of the anatase-phase nano titanium dioxide Li:Ti=0.75:1 that makes is added 20ml deionized water and 30ml alcohol, pour reactor into after fully stirring, and 120 ℃ were reacted 12 hours.Oven dry is annealed 400 ℃ after grinding, and namely obtains the titanium dioxide nano photocatalysis agent that lithium fluoride is modified.
The sample of getting the 0.1g modified joins in the methylene blue solution that 50ml concentration is 4mg/L, and ultrasonic processing is 10 minutes under dark surrounds, carries out testing adsorption effect.The result demonstration, adsorption efficiency was 92% in ultrasonic 10 minutes.
To adsorb 400 ℃ of lower annealing in process of sample 2 hours of methylene blue, the methylene blue solution of degrading under visible light, degradation rate can reach 60% in 4 hours.
Case study on implementation 3
The precursor solution for preparing titanic oxide nano powder is: deionized water 135ml, and concentration is 98% sulfuric acid 2.4ml, and concentration is 37% hydrochloric acid 1.85ml, and concentration is 98% butyl titanate 10ml.Dropwise add butyl titanate after acid and water are fully mixed, by magnetic agitation and fully mix, obtain faint yellow settled solution.Then solution is poured in reactor, put into 80 ℃ of hydro-thermal reactions of drying box after sealing 10 hours.To react the sediment that generates after the question response still is cooling and pour out, with deionized water, repeatedly rinse to neutrality, anatase phase titanium dioxide nanometer powder after oven dry is ground.
Lithium fluoride powder and the mol ratio of the anatase-phase nano titanium dioxide Li:Ti=1:1 that makes are added
The mixed solution of 20ml deionized water and 30ml alcohol, pour reactor into after fully stirring, and 120 ℃ were reacted 12 hours.Oven dry is annealed 400 ℃ after grinding, and namely obtains the titanium dioxide nano photocatalysis agent that lithium fluoride is modified.
The sample of getting the 0.1g modified joins in the methylene blue solution that 50ml concentration is 4mg/L, and ultrasonic processing is 10 minutes under dark surrounds, carries out testing adsorption effect.The result demonstration, adsorption efficiency was 87% in ultrasonic 10 minutes.
To adsorb 400 ℃ of lower annealing in process of sample 2 hours of methylene blue, the methylene blue solution of degrading under visible light, degradation rate can reach 57% in 4 hours.