CN109759042A - A kind of photochemical catalyst and its application to the degradation of different gaseous-phase organic pollutant high efficiency photocatalysis - Google Patents
A kind of photochemical catalyst and its application to the degradation of different gaseous-phase organic pollutant high efficiency photocatalysis Download PDFInfo
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Abstract
A kind of application the invention discloses photochemical catalyst and its to the degradation of different gaseous-phase organic pollutant high efficiency photocatalysis.The photochemical catalyst is the composite material of growth in situ titanium dioxide over celite.Preparation method are as follows: using titanium tetrachloride as titanium source, photochemical catalyst is prepared as solvent, by one step hydro thermal method as carrier, dehydrated alcohol in cellular diatomite.It is applied to the different gaseous-phase organic pollutants of processing, photocatalysis efficiency is high, process is simple, at low cost and the problem of secondary pollution is not present.The present invention solve the problems, such as conventional catalyst is poor to Adsorption of Organic ability, catalytic activity is weak, gas degradation difficulty be not thorough, have residual etc. it is a series of at present it is insoluble.The product has potential using value in directions such as the especially indoor gas phase organic contamination processing of photocatalytic applications, gaseous-phase organic pollutant processing, environment optimization, and is expected to industrialized production, is applied in living environment.
Description
Technical field
The invention belongs to photocatalytic degradation of organic matter technical field, in particular to a kind of photochemical catalyst and its to different gas phases
The application of organic pollutant high efficiency photocatalysis degradation.
Background technique
With industrialization, the quickening of Development of China's Urbanization, bring problem of environmental pollution is further serious.In course of industrialization
The pollution mainly generated is three industrial wastes-waste water,waste gas and industrial residue, gives the huge pressure of environment bring.Wherein, industrial waste gas
Refer to the various gases not used given off in industrial processes, including flue dust, foul smell, irritative gas and other have
Evil gas.Very big pollution is caused to environment for human survival.Other than this outdoor environment pollution problem of industrial waste gas, room
Environment pollution problem also can not be ignored.Room air pollution source includes outside contamination building and internal resource, such as Building wood
Material, perfume and cleaning products, solvent and glue, office machinery, culinary art, biology metabolism and smoking etc..According to world health group
Title is knitted, there is 3,800,000 people premature death due to the inefficient room air pollution for using solid fuel and generating with kerosene culinary art every year；?
In leukaemic, most of has been the room of rigid finishing soon.The room just fitted up can produce from construction material,
The organic gas of the new materials such as furniture.These have very major injury to human body, some even have carcinogenic, teratogenesis, mutagenesis.Its
In, volatile organic contaminant occupies sizable ratio.For this purpose, it is urgently to be resolved as one how to solve gaseous environment pollution
The problem of.The research of related photocatalysis technology processing gaseous-phase organic pollutant is increasingly taken seriously recently.Although scientists
Processing gaseous-phase organic pollutant in done many research, take many processing methods, as absorption method, condensing recovery method,
Direct combustion method, nanometer light electrolysis oxidizing process etc..But there is the problems such as at high cost, investment is big, degradation efficiency is not good enough mostly.Cause
This, designs the method that one kind is nontoxic, pollution-free, inexpensive, recovery efficiency is high and carves to handle gas phase organic contamination problem
Do not allow to delay.
TiO2Semiconductor has made it due to its structure and thermal stability, anticorrosive, inexpensive and pollution-free etc. excellent properties
It can be used for many fields, such as air, the purification of water pollution.Organic dirt difficult to degrade for being generated in industry especially dyestuff industry
It, can be by organic pollutant degradation difficult to degrade at small molecule compound when contaminating object.Most researchers are to TiO2In the liquid phase
Research it is more, but the research of vapor phase contaminants is related to seldom.Compared with the photocatalytic degradation of liquid-phase system, gas phase reaction body
System is simple, and by-product is few, and mineralising is easier to, and light utilization ratio is high.Therefore, TiO2In gaseous-phase organic pollutant degradation, tool
There is wide actual application prospect.But research of the current catalyst in gaseous-phase organic pollutant processing is less, degradation effect
It still needs to further study.Catalytic degradation principle:
In the degradation process to gaseous-phase organic pollutant, organic gas by oxidation-adsorption first on the surface of catalyst,
Finally it is converted into CO2And H2O, so that gaseous-phase organic pollutant be removed.During this, since the reactivity of catalyst is strong,
Catalysis reaction is more thorough.Its reaction principle is as follows: having semiconductor TiO in catalyst2, when being irradiated by light, according to partly leading
The electronic structure feature of body, when catalyst, which absorbs energy, is greater than or equal to the photon of its band gap, electrons are from being full of
Valence band transits to empty conduction band, thus a high activity electronics (e is generated on conduction band-), and positively charged sky is left in valence band
Cave (h+).Photoinduced electron has very strong reproducibility, so that the electron acceptor of semiconductor surface is reduced.Dissolved oxygen and water and electricity
Son and hole interaction, the final hydroxyl for generating high activity.OH-、O2 -、OOH-Free radical has strong oxidizing property, can be most
Number is adsorbed on TiO2The organic pollutant (acetone gas, benzene gas as involved in the present invention) on surface is degraded to CO2、H2O,
Inorganic pollution aoxidizes or is reduced to harmless object.
TiO2The Mechanism of Semiconductor Photocatalytic Degradation stage, which can summarize, is divided into following 7 steps to complete light-catalysed process:
1、TiO2+hv→e-+h+
2、h++H2O→OH+H+
3、e-+O2→O2 -
4、O2 -+H+→OOH
5、2OOH→O2+H2O2
6、O2 -+e-+2H+→H2O2
7、H2O2+e-→OH+OH-
8、h++OH-→OH
Summary of the invention:
For above situation, the present invention provides a kind of photochemical catalyst, under ultraviolet light or/and radiation of visible light, is answered
For degrading to different gaseous-phase organic pollutant high efficiency photocatalysis.The photochemical catalyst is growth in situ titanium dioxide over celite
Composite material, be applied to the different gaseous-phase organic pollutants of processing, photocatalysis efficiency is high, process is simple, it is at low cost and
And the problem of secondary pollution is not present.It is poor to Adsorption of Organic ability to solve conventional catalyst, catalytic activity is weak, gas
Degradation difficulty be not thorough, have residual etc. it is a series of at present insoluble problems.The product is in photocatalytic applications, the organic dirt of gas phase
There is highly important potential using value in the directions such as the especially indoor gas phase organic contamination processing of the processing of dye object, environment optimization,
And it is expected to industrialized production, is applied in living environment, which has important practical significance.
Photochemical catalyst of the present invention is the composite material of growth in situ titanium dioxide over celite.Preparation method
Are as follows: using titanium tetrachloride as titanium source, cellular diatomite is as carrier, and dehydrated alcohol is as solvent, by one step hydro thermal method system
It is standby to obtain photochemical catalyst.
Specific preparation process is as follows for photochemical catalyst of the present invention:
A, dehydrated alcohol 50.00mL is added in three-necked flask, is placed in ice-water bath and stirs 10-30min, then stirring
Under conditions of, 1-5.00mL titanium tetrachloride is added dropwise into three-necked flask, then takes 0.10-1.50mL water to be added with liquid-transfering gun
Wherein, continue stirring to formation yellow transparent solution；
B, it weighs 2.00-6.00g diatomite to be placed in 100mL reaction kettle, the yellow transparent solution that step A is obtained shifts
It into reaction kettle, stirs evenly, is put into 150-250 DEG C of reaction 10-20h in baking oven；
C, it after the reaction was completed, is washed 3-5 times respectively with dehydrated alcohol and deionized water, flushing to neutrality, later in an oven
60-80 DEG C of dry 5-15h.
The above-mentioned photochemical catalyst being prepared degrades to different gaseous-phase organic pollutant high efficiency photocatalysis.The light is urged
Change degradation specific reaction condition are as follows: photochemical catalyst is added in different gaseous-phase organic pollutants, under ultraviolet light/visible light into
Row photocatalytic degradation.
The different gaseous-phase organic pollutants are low boiling point gaseous-phase organic pollutant.
The different gaseous-phase organic pollutants are one or more of aromatic hydrocarbons, ketone and gaseous aldehyde.
The beneficial effects of the present invention are:
(1) present invention is using titanium tetrachloride as titanium source, using dehydrated alcohol as solvent, regulates and controls the ratio of diatomite and titanium dioxide
Example controls the temperature of reaction to control the hydrolysis rate of titanium tetrachloride, prepares light by easy one step hydro thermal method reaction and urge
Change the catalyst of function admirable.It is directly used in photocatalytic degradation difference gaseous-phase organic pollutant later.Whole experiment process is easy,
Nontoxic, pollution-free, at low cost, photocatalysis efficiency is high.
(2) present invention it is small to the selectivity of different gaseous-phase organic pollutants, be suitable for most of gaseous-phase organic pollutants and
Show good photocatalysis performance.
(3) biodegrading process is easy to industrialized production, and being suitable for indoor and outdoor reduces gaseous-phase organic pollutant concentration and harm.
There is boundless application prospect in terms of building, house ornamentation.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of photochemical catalyst made from embodiment one.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of photochemical catalyst made from embodiment two
Fig. 3 is the photocatalytic degradation curve of acetone gas in embodiment one.
Fig. 4 is the photocatalytic degradation curve of benzene gas in embodiment two.
Specific embodiment
Embodiment one
A, dehydrated alcohol 50.00mL is added in three-necked flask, is placed in ice-water bath and stirs 20min, in the condition of stirring
Under, it is slowly added to 2.00mL titanium tetrachloride dropwise to three-necked flask, then takes 0.50mL water to be added thereto with liquid-transfering gun, continues to stir
It mixes to yellow transparent solution；
B, it weighs 4.00g diatomite to be placed in 100mL reaction kettle, yellow transparent solution obtained in step A is transferred to
In reaction kettle, stir evenly in a reactor with diatomite by yellow transparent solution, it is put into 200 DEG C of reaction 12h of baking oven；
C, it after the reaction was completed, is washed respectively 4 times with dehydrated alcohol and deionized water, rinsing to pH is 7 or so, later in baking oven
In 80 DEG C of dry 10h obtain photochemical catalyst.
The photochemical catalyst of above method preparation is subjected to photocatalytic degradation.0.05g photochemical catalyst is weighed in head space air-tight bottle
In, a certain amount of acetone gas is added to it with gas phase sample introduction needle, photocatalytic degradation is carried out under ultraviolet light/visible light.Used
The following Fig. 1 of the scanning electron microscope (SEM) photograph of photochemical catalyst.
In degradation process, per a sample is taken at regular intervals, quantitative and qualitative analysis, co-degradation 3- are carried out to sample
6h.The control of degradation gas concentration is that 1mL saturation acetone gas is taken to be injected separately into different volumes by using gas phase sample introduction needle
Airtight bottle in.Wherein, 100mL1 airtight bottle is denoted as 100mL (1), and 100mL2 airtight bottle is denoted as 100mL (2), 200mL1
Number airtight bottle is denoted as 200mL (1), 200mL2 airtight bottle is denoted as 200mL (2), 500mL1 airtight bottle is denoted as 500mL1),
500mL2 airtight bottle is denoted as 500mL (2).Catabolite using GC-MS joint technology to the quantitative of the organic gas of degradation and
Qualitative analysis.Degradation results are analyzed as follows shown in Fig. 2, generate good catalytic effect to acetone gas.30min, 60min,
There is obvious degradation trend in 90min, in 120min, acetone gas is substantially completely degraded.Get off in whole process, degradation effect
Rate is up to 100%.
Embodiment two
A, dehydrated alcohol 50.00mL is added in three-necked flask, is placed in ice-water bath and stirs 20min, in the condition of stirring
Under, it is slowly added to 2.00mL titanium tetrachloride dropwise to three-necked flask, then takes 0.50mL water to be added thereto with liquid-transfering gun, continues to stir
It mixes to yellow transparent solution；
B, it weighs 4.00g diatomite to be placed in 100mL reaction kettle, yellow transparent solution obtained in step A is transferred to
In reaction kettle, stir evenly in a reactor with diatomite by yellow transparent solution, it is put into 200 DEG C of reaction 12h of baking oven；
C, it after the reaction was completed, is washed respectively 4 times with dehydrated alcohol and deionized water, rinsing to pH is 7 or so, later in baking oven
In 80 DEG C of dry 10h obtain photochemical catalyst.
The photochemical catalyst of above method preparation is subjected to photocatalytic degradation.0.05g photochemical catalyst is weighed in head space air-tight bottle
In, a certain amount of benzene gas is added to it with gas phase sample introduction needle, photocatalytic degradation is carried out under ultraviolet light/visible light.Light used
The following Fig. 1 of the scanning electron microscope (SEM) photograph of catalyst.
In degradation process, per a sample is taken at regular intervals, quantitative and qualitative analysis, co-degradation 3- are carried out to sample
6h.The control of degradation gas concentration is that 1mL saturation benzene gas is taken to be injected separately into different volumes by using gas phase sample introduction needle
In airtight bottle.Wherein, 100mL1 airtight bottle is denoted as 100mL (1), and 100mL2 airtight bottle is denoted as 100mL (2), No. 200mL1
Airtight bottle is denoted as 200mL (1), 200mL2 airtight bottle is denoted as 200mL (2), 500mL1 airtight bottle is denoted as 500mL1),
500mL2 airtight bottle is denoted as 500mL (2).Catabolite using GC-MS joint technology to the quantitative of the organic gas of degradation and
Qualitative analysis.Degradation results are analyzed as follows shown in Fig. 3, generate good catalytic effect to benzene gas.In entire degradation process,
Benzene gas is degraded, and trend is obvious, and degradation efficiency is very high.
Claims (7)
1. a kind of photochemical catalyst, which is characterized in that the photochemical catalyst is answered for growth in situ titanium dioxide over celite
Condensation material.
2. the preparation method of photochemical catalyst according to claim 1, which is characterized in that its preparation condition are as follows: with four chlorinations
Photocatalysis is prepared as solvent, by one step hydro thermal method as carrier, dehydrated alcohol as titanium source, cellular diatomite in titanium
Agent.
3. preparation method according to claim 2, which is characterized in that specific preparation process is as follows for it:
A, dehydrated alcohol 50.00mL is added in three-necked flask, is placed in ice-water bath and stirs 10-30min, then in the item of stirring
Under part, 1-5.00mL titanium tetrachloride is added dropwise into three-necked flask, then takes 0.10-1.50mL water that it is added with liquid-transfering gun
In, continue stirring to formation yellow transparent solution；
B, it weighs 2.00-6.00g diatomite to be placed in 100mL reaction kettle, the obtained yellow transparent solution of step A is transferred to instead
It answers in kettle, stirs evenly, be put into 150-250 DEG C of reaction 10-20h in baking oven；
C, it after the reaction was completed, is washed 3-5 times, is rinsed to neutrality respectively with dehydrated alcohol and deionized water, later 60-80 in an oven
DEG C dry 5-15h.
4. different gaseous-phase organic pollutant high efficiency photocatalysis drop in the photochemical catalyst that method is prepared according to claim 3
The application of solution.
5. application according to claim 4, which is characterized in that the specific reaction condition of the photocatalytic degradation are as follows: will
Photochemical catalyst is added in different gaseous-phase organic pollutants, and photocatalytic degradation is carried out under ultraviolet light/visible light.
6. application according to claim 5, which is characterized in that the different gaseous-phase organic pollutants are low boiling point gas phase
Organic pollutant.
7. application according to claim 5, which is characterized in that the different gaseous-phase organic pollutants are aromatic hydrocarbons, ketone
One or more of with gaseous aldehyde.
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