CN101654397A - Method for catalyzing and reducing ethanol with carbon dioxide under visible light - Google Patents

Method for catalyzing and reducing ethanol with carbon dioxide under visible light Download PDF

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Publication number
CN101654397A
CN101654397A CN200910018659A CN200910018659A CN101654397A CN 101654397 A CN101654397 A CN 101654397A CN 200910018659 A CN200910018659 A CN 200910018659A CN 200910018659 A CN200910018659 A CN 200910018659A CN 101654397 A CN101654397 A CN 101654397A
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bivo
water
solution
gas
visible light
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CN101654397B (en
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黄柏标
刘媛媛
张晓阳
秦晓燕
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Shandong University
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Shandong University
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Abstract

The invention provides a method for catalyzing and reducing ethanol with carbon dioxide under visible light. The method comprises the following steps: (1) dissolving Bi(NO3)3.5H2O in nitric acid and adding CTAB, further dissolving NH4VO3 in sodium hydroxide and adding CTAB, then separately stirring the two prepared solutions at room temperature for 30min, mixing the two solutions, adjusting the pHvalue of the mixed solution to 7, heating with microwave to 200 DEG C for 40min, cooling to room temperature, washing the obtained product with deionized water to remove CTAB in the mixed solution, drying to obtain monoclinic BiVO4; (2) dispersing BiVO4 in water, then injecting CO2 gas on the condition of magnetic stirring while cooling with ice water mixture and obtaining ethanol, wherein when injecting CO2 gas, a 36W daylight lamp, a 300W high pressure xenon lamp or a 300W high pressure xenon lamp of which less than 400nm of ultraviolet is leached is used to irradiate the system and the illumination time is 80-100min. The method of the invention has low cost and the catalyst BiVO4 can be recyled.

Description

The carbon dioxide under visible light catalytic reduction is the alcoholic acid method
Technical field
The present invention relates to a kind ofly be converted into the alcoholic acid method as carbon source, belong to the category of conductor photocatalysis with carbonic acid gas.
Background technology
In recent decades, the problem of environmental pollution that discharging wastes causes causes the concern in the world gradually, the global warming that causes as the excessive emissions of greenhouse gases.CO 2Be a kind of important greenhouse gases.At present, reduce CO 2Discharging mainly contain two kinds of development trends: the one, reduce CO from root 2Discharging, as using green energy resources such as hydrogen, electric power; The 2nd, to CO 2Catch and change into carbonaceous organism.According to present state of the art, the exploitation green energy resource is bigger than the latter's difficulty, how effectively to catch CO 2Further convert it into organism then and seem even more important.
Existing bibliographical information is crossed and is utilized semiconductor light-catalyst with CO 2Be converted into methyl alcohol, methane, formic acid and acetate etc.Ethanol is a kind of important common organic compounds, has purposes quite widely, not only can be used as fuel, also is a kind of important industrial raw material, and as make acetate, ether etc. with ethanol, the ethanol of 75% (volume fraction) commonly used is made sterilizing agent etc. in the medical treatment.People such as Japan scientist T.Muzuno find TiO 2Photoreduction CO in the sodium hydroxide solution of alkalescence 2The time can generate small amount of ethanol (T.Mizuno, K.Adachi, K.Ohta, A.Saji, Effect of CO 2Pressure on photocatalytic reductionof CO 2Using TiO 2In aqueous solutions, Journal of Photochemistry.and PhotobiologyA:Chemistry 98 (1996) 87-90 (Mizuno, K.Adachi, K.Ohta, A.Saji, " pressure carbon dioxide is to the influence of photocatalysis performance when using the optically catalytic TiO 2 reducing carbon dioxide in the aqueous solution ", " photochemistry and photobiology " magazine .A collects, chemistry 98 (1996) 87-90).But this method needs under high pressure, and (2.5MPa) carries out, long reaction time (24 hours), and generate alcoholic acid amount also less (tens μ mol).
Summary of the invention
Utilize semiconductor light-catalyst with CO at existing 2Be converted into the deficiency that the ethanol technology exists, the carbonic acid gas catalytic reduction that the invention provides that a kind of cost is low, catalyzer recyclablely utilizes again, visible light drives and normal pressure is implemented down is the alcoholic acid method.
Carbon dioxide under visible light catalytic reduction of the present invention is the alcoholic acid method, is to utilize semiconductor light-catalyst BiVO 4, under the effect of visible light, realize the CO in the water medium 2Change into ethanol, specifically may further comprise the steps:
(1) photocatalyst BiVO 4Preparation
Prepare the Bi (NO of volumetric molar concentrations such as equal-volume respectively 3) 3.5H 2O solution and NH 4VO 3Solution, wherein Bi (NO 3) 3.5H 2O 4mol L -1Salpeter solution dissolving, NH 4VO 3Use 2mol L -1Sodium hydroxide solution dissolving, in two kinds of solution of preparation, add cetyl trimethylammonium bromide (CTAB) respectively, make the concentration of cetyl trimethylammonium bromide in two kinds of solution be 6.8 * 10 -2MolL -1After stirring half an hour separately under two kinds of solution room temperatures, mix then, the pH value of mixing solutions is adjusted to 7, after continuing to stir half an hour, mixing solutions is poured in the polytetrafluoroethyllining lining reactor, microwave heating to 200 ℃, heated 40 minutes, and naturally cooled to room temperature then, with deionized water the cetyl trimethylammonium bromide in the mixing solutions is thoroughly washed off again, dried 4 hours down at 100 ℃, obtain monocline phase BiVO 4
(2) BiVO 4To CO 2Photo catalytic reduction
By every gram BiVO 4The ratio that adds 500ml water is with BiVO 4Be dispersed in the water, then under magnetic agitation with 0.4 liter/minute speed to being dispersed with BiVO 4Water in feed CO 2Gas, the beaker that the above-mentioned aqueous solution will be housed simultaneously cools off with mixture of ice and water, to increase CO 2Solubleness in water and the volatilization of inhibition resultant alcoholic acid feed CO 2In the time of gas, be dispersed with BiVO with 36W fluorescent lamp, 300W high pressure xenon lamp or the 300W high pressure xenon lamp irradiation that filters the following UV-light of 400nm 4The aqueous solution, light application time 80 minutes-100 minutes can generate ethanol.
Method of the present invention can be implemented under visible light driving and normal pressure, weak point consuming time, and cost is low, and equipment is simple to operation, and semiconductor light-catalyst BiVO 4Can pass through the suction filtration recycling, have important potential application aspect environmental improvement and the industrial production.
Embodiment
Embodiment 1
(1) photocatalyst BiVO 4Synthetic: with 4.9g Bi (NO 3) 3.5H 2O (10mmol) is dissolved in 20ml4mol L -1Nitric acid in, add 0.5g cetyl trimethylammonium bromide (CTAB); 1.16g (10mmol) NH 4VO 3Be dissolved in 20ml2mol L -1Sodium hydroxide in, add 0.5g CTAB.Mix after respectively stirring half an hour under the solution room temperature for preparing, use 2mol L -1Sodium hydroxide adjust pH to 7.After continue stirring half an hour, mixed solution is poured in the polytetrafluoroethyllining lining reactor, microwave heating to 200 ℃ was heated 40 minutes.Behind the cool to room temperature, CTAB is thoroughly washed off with deionized water.Dried 4 hours for 100 ℃.Obtain monocline phase BiVO 4
(2) with 0.2g BiVO 4Be dispersed in the 100ml water constantly logical CO under the magnetic agitation 2Gas (speed is 0.4 liter/minute).(purpose is to increase CO to whole system with the mixture of ice and water cooling 2Solubleness in water and the volatilization of inhibition resultant alcoholic acid).Logical CO 2In the time of gas, shine above-mentioned system with the 36W fluorescent lamp.
(3) illumination was taken out 3ml liquid, centrifugation (3000r/min) after 80 minutes.Supernatant liquid gas chromatographic detection reduzate (fid detector, VF-5ms capillary column).Generating the alcoholic acid amount is 3.1 μ mol.
Embodiment 2
(1) photocatalyst BiVO 4Synthetic: detailed process is identical with embodiment 1.
(2) with 0.2g BiVO 4Be dispersed in the 100ml water constantly logical CO under the magnetic agitation 2Gas (speed is 0.4 liter/minute).System is cooled off with mixture of ice and water.Logical CO 2In the time of gas, with 300W high pressure xenon lamp irradiation (filtering the following UV-light of 400nm) above-mentioned system.
(3) behind the illumination 80min, take out 3ml liquid, centrifugation (3000r/min).Supernatant liquid gas chromatographic detection reduzate (fid detector, VF-5ms capillary column).Generating the alcoholic acid amount is 28.6 μ mol.
Embodiment 3
(1) photocatalyst BiVO 4Synthetic: detailed process is identical with embodiment 1.
(2) with 0.2g BiVO 4Be dispersed in the 100ml water constantly logical CO under the magnetic agitation 2Gas (speed is 0.4 liter/minute).System is cooled off with mixture of ice and water.Logical CO 2In the time of gas, shine above-mentioned system with the 300W high pressure xenon lamp.
(3) illumination was taken out 3ml liquid, centrifugation (3000r/min) after 90 minutes.Supernatant liquid gas chromatographic detection reduzate (fid detector, VF-5ms capillary column).Generating the alcoholic acid amount is 550.0 μ mol.
Embodiment 4
(1) photocatalyst BiVO 4Synthetic: detailed process is identical with embodiment 1.
(2) with 0.2g BiVO 4Be dispersed in the 100ml water constantly logical CO under the magnetic agitation 2Gas (speed is 0.4L/min).System is cooled off with mixture of ice and water.Logical CO 2In the time of gas, shine above-mentioned system with the 300W high pressure xenon lamp.
(3) illumination was taken out 3ml liquid, centrifugation (3000r/min) after 100 minutes.Supernatant liquid gas chromatographic detection reduzate (fid detector, VF-5ms capillary column).Generating the alcoholic acid amount is 545.0 μ mol.

Claims (1)

1. a carbon dioxide under visible light catalytic reduction is the alcoholic acid method, is to utilize semiconductor light-catalyst BiVO 4, under the effect of visible light, realize the CO in the water medium 2Change into ethanol, specifically may further comprise the steps:
(1) photocatalyst BiVO 4Preparation
Prepare the Bi (NO of volumetric molar concentrations such as equal-volume respectively 3) 3.5H 2O solution and NH 4VO 3Solution, wherein Bi (NO 3) 3.5H 2O 4mol L -1Salpeter solution dissolving, NH 4VO 3Use 2mol L -1Sodium hydroxide solution dissolving, in two kinds of solution of preparation, add cetyl trimethylammonium bromide (CTAB) respectively, make the concentration of cetyl trimethylammonium bromide in two kinds of solution be 6.8 * 10 -2MolL -1After stirring half an hour separately under two kinds of solution room temperatures, mix then, the pH value of mixing solutions is adjusted to 7, after continuing to stir half an hour, mixing solutions is poured in the polytetrafluoroethyllining lining reactor, microwave heating to 200 ℃, heated 40 minutes, and naturally cooled to room temperature then, with deionized water the cetyl trimethylammonium bromide in the mixing solutions is thoroughly washed off again, dried 4 hours down at 100 ℃, obtain monocline phase BiVO 4
(2) BiVO 4To CO 2Photo catalytic reduction
By every gram BiVO 4The ratio that adds 500ml water is with BiVO 4Be dispersed in the water, then under magnetic agitation with 0.4 liter/minute speed to being dispersed with BiVO 4Water in feed CO 2Gas, the beaker that the above-mentioned aqueous solution will be housed simultaneously cools off with mixture of ice and water, to increase CO 2Solubleness in water and the volatilization of inhibition resultant alcoholic acid feed CO 2In the time of gas, be dispersed with BiVO with 36W fluorescent lamp, 300W high pressure xenon lamp or the 300W high pressure xenon lamp irradiation that filters the following UV-light of 400nm 4The aqueous solution, light application time 80 minutes-100 minutes promptly generates ethanol.
CN2009100186599A 2009-09-09 2009-09-09 Method for catalyzing and reducing ethanol with carbon dioxide under visible light Expired - Fee Related CN101654397B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101791548A (en) * 2010-04-22 2010-08-04 华中科技大学 Visible light catalyst BiVO4 and preparation method thereof
CN101869821A (en) * 2010-07-14 2010-10-27 西北大学 External circulation enclosed photocatalytic reduction CO2 reaction device
CN102125832A (en) * 2011-01-19 2011-07-20 南京理工大学 Visible light responsive pucherite-graphene composite photocatalyst and preparation method thereof
CN102230274A (en) * 2011-05-13 2011-11-02 东华大学 Low-temperature in-situ synthesis method for preparing BiVO4 composite fabric which has function of air cleaning
CN102275988A (en) * 2011-05-24 2011-12-14 陕西科技大学 Microwave hydrothermal method for synthesizing monoclinic-phase bismuth vanadate photocatalyst powder
CN102295311A (en) * 2011-07-22 2011-12-28 河北联合大学 Method for preparing bismuth vanadate nano-material by microwave radiation method
CN103074761A (en) * 2013-01-22 2013-05-01 东华大学 Method for preparing upholstery multifunctional air purification function fabric for public transport means
CN105332002A (en) * 2015-12-13 2016-02-17 兰州大学 Method for preparing ethyl alcohol through carbon dioxide and water

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007037321A1 (en) * 2005-09-29 2007-04-05 Sumitomo Metal Industries, Ltd. Titanium oxide photocatalyst, method for producing same and use thereof
CN100488625C (en) * 2007-06-28 2009-05-20 北京工业大学 Method for preparing nanometer BiVO4 material visible-light photocatalyst

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101791548A (en) * 2010-04-22 2010-08-04 华中科技大学 Visible light catalyst BiVO4 and preparation method thereof
CN101869821A (en) * 2010-07-14 2010-10-27 西北大学 External circulation enclosed photocatalytic reduction CO2 reaction device
CN102125832A (en) * 2011-01-19 2011-07-20 南京理工大学 Visible light responsive pucherite-graphene composite photocatalyst and preparation method thereof
CN102125832B (en) * 2011-01-19 2013-06-05 南京理工大学 Visible light responsive pucherite-graphene composite photocatalyst and preparation method thereof
CN102230274A (en) * 2011-05-13 2011-11-02 东华大学 Low-temperature in-situ synthesis method for preparing BiVO4 composite fabric which has function of air cleaning
CN102230274B (en) * 2011-05-13 2013-01-16 东华大学 Low-temperature in-situ synthesis method for preparing BiVO4 composite fabric which has function of air cleaning
CN102275988A (en) * 2011-05-24 2011-12-14 陕西科技大学 Microwave hydrothermal method for synthesizing monoclinic-phase bismuth vanadate photocatalyst powder
CN102275988B (en) * 2011-05-24 2013-12-25 陕西科技大学 Microwave hydrothermal method for synthesizing monoclinic-phase bismuth vanadate photocatalyst powder
CN102295311A (en) * 2011-07-22 2011-12-28 河北联合大学 Method for preparing bismuth vanadate nano-material by microwave radiation method
CN102295311B (en) * 2011-07-22 2013-12-04 河北联合大学 Method for preparing bismuth vanadate nano-material by microwave radiation method
CN103074761A (en) * 2013-01-22 2013-05-01 东华大学 Method for preparing upholstery multifunctional air purification function fabric for public transport means
CN105332002A (en) * 2015-12-13 2016-02-17 兰州大学 Method for preparing ethyl alcohol through carbon dioxide and water

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