Summary of the invention
For the above-mentioned problems in the prior art, one is the object of the present invention is to provide to have absorption and degrade difunctional, and the preparation method of the fast TiO2 load nitrogen-doped graphene sponge of high adsorption capacity, degradation speed and application thereof.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, it is characterized in that preparation method is as follows: add containing titanium precursors in the alcohol dispersion liquid containing graphene oxide, slowly drip deionized water again, stir formation mixed liquor, carry out hydro-thermal reaction 12 ~ 48 hours at 180 ~ 240 DEG C, it is shaping to take out freeze drying under-80 ~-75 DEG C of conditions, then proceeds to logical high-purity nitrogenous gas in vacuum tube furnace, and to be warming up in 400 ~ 800 DEG C roasting 3 ~ 12 hours, obtain containing 5 ~ 10%TiO
2three-dimensional porous nitrogen-doped graphene sponge.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, is characterized in that the concentration of graphene oxide in the alcohol dispersion liquid containing graphene oxide is 1-2mg/ml.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, it is characterized in that the time for adding of deionized water is 30-60min, the hydro-thermal reaction time is 20-24 hour.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, it is characterized in that the flow of logical high-purity nitrogenous gas is 100ml/ minute, programming rate is 5 DEG C/min.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, to it is characterized in that in described 400 ~ 800 DEG C logical high-purity nitrogenous gas 3 ~ 12 hours, sintering temperature is 600 ~ 750 DEG C, and roasting time is 3 ~ 4 hours.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, is characterized in that described is butyl titanate or titanium tetrachloride containing titanium precursors.
Described a kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, is characterized in that described preparation method is specific as follows:
1) alcohol dispersion liquid of the graphene oxide containing 1-2 mg/ml is measured, add containing titanium precursors, more slowly drip deionized water, form mixed liquor, stir, the alcohol dispersion liquid of described graphene oxide, butyl titanate and the deionized water volume ratio that feeds intake is 45-55:5:2
2) mixed liquor that step 1) obtains is poured in hydrothermal reaction kettle, carry out hydro-thermal reaction 12 ~ 48 hours at 180 ~ 240 DEG C, then naturally cool, obtain TiO
2the Graphene gel of load;
3) by step 2) Graphene gel that obtains-80 ~-75 DEG C of frozen dryings 24 hours, obtain three-dimensional porous TiO
2load graphene sponge;
4) step 3) is obtained three-dimensional porous TiO
2load graphene sponge is placed in vacuum tube furnace, passes into high-purity nitrogenous gas by the flow of 100ml/min, to be warming up in 400 ~ 800 DEG C roasting 3 ~ 12 hours by 5 DEG C/min, namely obtains containing 4 ~ 5 % TiO
2the nitrogen-doped graphene sponge of load.
Described TiO
2the application of load nitrogen-doped graphene sponge in absorbed air in formaldehyde or benzene-like compounds.
Described TiO
2the application of load nitrogen-doped graphene sponge, after it is characterized in that formaldehyde adsorption or benzene-like compounds, then is degraded to carbon dioxide, water by photocatalysis by formaldehyde or benzene-like compounds.
Described TiO
2the application of load nitrogen-doped graphene sponge, is characterized in that described benzene-like compounds comprises benzene, toluene and phenol.
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) TiO of the present invention
2the preparation of load nitrogen-doped graphene sponge forms compound by original position preparation, and it is simple to operate, low for equipment requirements, can be widely used in industrial production;
2) TiO of the present invention
2load nitrogen-doped graphene sponge has difunctional effect, both can strong adsorption formaldehyde or benzene-like compounds gas, make it be degraded to the nontoxic gases such as carbon dioxide by photocatalysis fast degradation simultaneously, realize the object purified air efficiently, rapidly, there is the unique advantage in performance;
3) TiO of the present invention
2load nitrogen-doped graphene sponge by straightforward procedure activating and regeneratings such as washing, roastings, reusing, because this reducing use cost, improve economic benefit after using certain hour;
4) TiO of the present invention
2preparation method is simple for load nitrogen-doped graphene sponge, it has dual-use function, both adsorbable a large amount of formaldehyde or benzene-like compounds gas, and can pass through formaldehyde degradation by photocatalytic oxidation process or benzene-like compounds gas under ultra violet lamp, realize the object purified air efficiently, rapidly, be suitable for applying.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in this:
A kind of TiO
2the preparation method of load nitrogen-doped graphene sponge, specific as follows: to add containing titanium precursors in the alcohol dispersion liquid containing 1-2mg/ml graphene oxide, slower in 30-
Deionized water is dripped in 60min, stir formation mixed liquor, hydro-thermal reaction is carried out 12 ~ 48 hours at 180 ~ 240 DEG C, the preferred reaction time is 20-24 hour, it is shaping that reaction terminates rear taking-up freeze drying under-80 ~-75 DEG C of conditions, proceed to again in vacuum tube furnace and lead to high-purity nitrogenous gas with the flow of 100ml/ minute, and with roasting in gradient increased temperature to 400 ~ 800 of 5 DEG C/min DEG C 3 ~ 12 hours, preferred sintering temperature is 600 ~ 750 DEG C, preferred roasting time is 3 ~ 4 hours, obtains containing 5 ~ 10%TiO
2three-dimensional porous nitrogen-doped graphene sponge.
In the present invention, described is butyl titanate or titanium tetrachloride containing titanium precursors, and high-purity nitrogenous gas is nitrogen or ammonia, and its purity is more than 99.9%, and the alcohol dispersion liquid of graphene oxide, butyl titanate and the deionized water volume ratio that feeds intake is 45-55:5:2
The TiO that the present invention obtains
2load nitrogen-doped graphene sponge, has difunctional effect, and it not only can the benzene-like compounds such as formaldehyde or benzene, toluene and phenol in absorbed air, also by photocatalysis, the formaldehyde be adsorbed onto or benzene-like compounds is degraded to carbon dioxide, water, and TiO
2load nitrogen-doped graphene sponge can pass through roasting, regeneration continues to utilize.
embodiment 1:5%TiO
2the preparation method of load nitrogen-doped graphene sponge is as follows:
1) measure the alcohol dispersion liquid of 50 ml containing the graphene oxide of 2 mg/ml, and add 5ml butyl titanate, then in 30min, drip 2ml deionized water, form mixed liquor, stir;
2) mixed liquor is poured in 100ml hydrothermal reaction kettle, 180 DEG C of isothermal reactions 24 hours, then naturally cool, turn on hydrothermal reaction kettle and can obtain TiO
2the Graphene gel of load;
3) by the Graphene gel that obtains-78 DEG C of frozen dryings 24 hours, three-dimensional porous TiO can be obtained
2load graphene sponge;
4) three-dimensional porous TiO will be obtained
2load graphene sponge is placed in vacuum tube furnace, passes into high-purity ammonia (99.999%) by the flow of 100ml/min, is warming up to 600 DEG C of roastings 3 hours by 5 DEG C/min, can obtain containing 5%TiO
2the nitrogen-doped graphene sponge of load.
Application: will obtain containing 5%TiO
2the nitrogen-doped graphene sponge of load puts into 100ml photo catalysis reactor, drops into 0.3mg/M
3formaldehyde, get gas GC in reactor after sealing in half an hour and analyze content of formaldehyde, now show that content of formaldehyde is 0.2 mg/M
3, illustrate that nitrogen-doped graphene sponge PARA FORMALDEHYDE PRILLS(91,95) gas of the present invention has certain suction-operated, then carry out illumination experiment with the uviol lamp of 30W again, 2 hours complete by the Degradation Formaldehyde in reactor.
In this embodiment, replace butyl titanate containing titanium precursors titanium tetrachloride, high-purity nitrogenous gas nitrogen replaces ammonia, all can obtain same technique effect.
embodiment 2:6%tiO
2the preparation method of load nitrogen-doped graphene sponge is as follows:
1) measure the alcohol dispersion liquid of 45ml containing the graphene oxide of 1mg/ml, and add 5ml titanium tetrachloride, then in 60min, drip 2ml deionized water, form mixed liquor, stir;
2) mixed liquor is poured in 100ml hydrothermal reaction kettle, 200 DEG C of isothermal reactions 24 hours, then naturally cool, turn on hydrothermal reaction kettle and can obtain TiO
2the Graphene gel of load;
3) by the Graphene gel that obtains-80 DEG C of frozen dryings 24 hours, three-dimensional porous TiO can be obtained
2load graphene sponge;
4) three-dimensional porous TiO will be obtained
2load graphene sponge is placed in vacuum tube furnace, passes into high pure nitrogen (99.999%) by the flows of 100 ml/ minutes, is warming up to 400 DEG C of roastings 12 hours, can obtains 6%TiO by 5 DEG C/min
2the nitrogen-doped graphene sponge of load;
5) 4%TiO will be obtained
2the nitrogen-doped graphene sponge of load puts into homemade photo catalysis reactor, drops into 0.5mg/M
3toluene, get gas GC in reactor after sealing in half an hour and analyze toluene level, now show that toluene level is 0.35 mg/M
3, illustrate that nitrogen-doped graphene sponge has certain suction-operated to toluene gas.Then carry out illumination experiment with the uviol lamp of 50W again, 4 hours complete by the degradation of toluene in reactor.
embodiment 3:7%TiO
2the preparation method of load nitrogen-doped graphene sponge is as follows:
1) measure the alcohol dispersion liquid of 55 ml containing the graphene oxide of 1.5mg/ml, and add 6ml titanium tetrachloride, then drip 2.5 ml deionized waters in 45min, form mixed liquor, stir;
2) mixed liquor is poured in 100ml hydrothermal reaction kettle, 180 DEG C of isothermal reactions 48 hours, then naturally cool, turn on hydrothermal reaction kettle and can obtain TiO
2the Graphene gel of load;
3) by the Graphene gel that obtains-75 DEG C of frozen dryings 48 hours, three-dimensional porous TiO can be obtained
2load graphene sponge;
4) three-dimensional porous TiO will be obtained
2load graphene sponge is placed in vacuum tube furnace, passes into high pure nitrogen (99.999%) by the flows of 100 ml/ minutes, is warming up to 800 DEG C of roastings 3 hours, can obtains 7%TiO by 5 DEG C/min
2the nitrogen-doped graphene sponge of load;
5) 7%TiO will be obtained
2the nitrogen-doped graphene sponge of load puts into photo catalysis reactor, drops into 0.2mg/M
3phenol, get gas GC analysis of Phenol content in reactor after sealing in half an hour, now show that phenol content is 0.35 mg/M
3, illustrate that nitrogen-doped graphene sponge Pyrogentisinic Acid gas has certain suction-operated.Then carry out illumination experiment with the uviol lamp of 50W again, 3 hours complete by the phenol degrading in reactor.
embodiment four:5%TiO
2the preparation method of load nitrogen-doped graphene sponge is as follows:
1) measure the alcohol dispersion liquid of 50ml containing the graphene oxide of 2mg/ml, and add 6ml butyl titanate, then drip 2.5 ml deionized waters in 50min, form mixed liquor, stir;
2) mixed liquor is poured in 100ml hydrothermal reaction kettle, 240 DEG C of isothermal reactions 12 hours, then naturally cool, turn on hydrothermal reaction kettle and can obtain TiO
2the Graphene gel of load;
3) by the Graphene gel that obtains-78 DEG C of frozen dryings 48 hours, three-dimensional porous TiO can be obtained
2load graphene sponge;
4) three-dimensional porous TiO will be obtained
2load graphene sponge is placed in vacuum tube furnace, passes into high-purity ammonia (99.999%) by the flows of 100 ml/ minutes, is warming up to 700 DEG C of roastings 4 hours, can obtains 5%TiO by 5 DEG C/min
2the nitrogen-doped graphene sponge of load.
By the 5%TiO obtained
2the nitrogen-doped graphene sponge of load puts into photo catalysis reactor, drops into 0.3mg/M
3formaldehyde and 0.3mg/M
3toluene, to get in reactor gas GC after sealing in half an hour and analyze formaldehyde and toluene level, now show that content of formaldehyde is 0.25 mg/M
3, toluene level is 0.2mg/M
3.Then carry out illumination experiment with the uviol lamp of 50W again, 4 hours by the formaldehyde in reactor and degradation of toluene complete.
The preparation method of a kind of TiO2 load nitrogen-doped graphene sponge of the present invention is simple, this material obtained has dual-use function, solves in currently available technology and adsorbs saturation problem, can degrade while absorption, until toxic gas is adsorbed completely, reach the object purified air rapidly.