CN105332002B - A kind of method that ethanol is prepared by carbon dioxide and water - Google Patents

A kind of method that ethanol is prepared by carbon dioxide and water Download PDF

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Publication number
CN105332002B
CN105332002B CN201510914432.8A CN201510914432A CN105332002B CN 105332002 B CN105332002 B CN 105332002B CN 201510914432 A CN201510914432 A CN 201510914432A CN 105332002 B CN105332002 B CN 105332002B
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photocathode
tio
dye
ethanol
carbon dioxide
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CN105332002A (en
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景欢旺
张雨倩
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Lanzhou University
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Lanzhou University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections

Abstract

The present invention discloses a kind of method and used related device preparation method and device that ethanol is prepared with carbon dioxide and water.The method that the present invention prepares ethanol is：BiVO will be used4The light anode and composition dye/M/N TiO of composition2Or dye/M/B TiO2Or dye/M/S TiO2Photocathode be respectively placed in the KHCO containing sensitizer3Or NaHCO3In the electrolyte that the aqueous solution is formed, and light anode and time interpolar is set to keep an interval, light anode and photocathode are connected with the positive pole and negative pole of dc source respectively, carbon dioxide is filled with electrolyte, dc source is set to be powered to light anode, photocathode, make light source irradiation light anode and photocathode simultaneously, ethanol can be both generated in electrolyte.

Description

A kind of method that ethanol is prepared by carbon dioxide and water
Technical field
The present invention relates to related device preparation method and device used in a kind of preparation method of ethanol and this method, Particularly a kind of method and used related device preparation method and device that ethanol is prepared with carbon dioxide and water.
Background technology
Ethanol is important industrial chemicals or fuel, while can also be beverage.At present, preparing ethanol has two approach, Both fermentation method prepared or obtained ethene by the method for catalysis hydration.Fermentation method of the prior art is mainly for the production of edible Alcohol or alcoholic drink, this method need to consume a large amount of cereal, also have using stalk or the preparation of other fermentation of biomaterials Ethanol, such as authorize in the CN1006902 Chinese patents of the authorization of nineteen ninety 2 month 21 and on May 20th, 2015 CN103509828B Chinese patents.Ethylene hydration rule of the prior art needs HTHP, and its preparation condition is harsh, need to disappear Consume mass energy.
The content of the invention
The present invention provides a kind of method for being totally different from prior art and prepares ethanol, i.e., directly by water under illumination condition The method of the ethanol water of high-purity is made by electrical combined catalysis high efficiency with carbon dioxide, present invention simultaneously provides this The preparation method and device of Primary Component involved by one method.
The present invention it is a kind of ethanol is prepared by carbon dioxide and water method be：The BiVO that will be adulterated with Co-P modifications and W4 Light anode that electrode is formed and deposited by dye sensitization, transition metal and TiO through modification2The photocathode that electro-conductive glass is formed It is respectively placed in the KHCO containing sensitizer3Or NaHCO3In the electrolyte that the aqueous solution is formed, and keep light anode and time interpolar One interval, light anode and photocathode are connected with the positive pole and negative pole of dc source respectively, dioxy is filled with electrolyte Change carbon gas, dc source is powered to light anode, photocathode, while make light source irradiation light anode and photocathode, keep this State, and the supplement carbon dioxide in good time in electrolyte, ethanol can be both generated in electrolyte, obtained electrolyte is entered Row rectifying obtains ethanol water.
In a kind of embodiment of method that ethanol is prepared by carbon dioxide and water of the present invention, by dye sensitization, transition gold Category deposition and modification TiO2The photocathode that electro-conductive glass is formed is dye sensitization, transition metal deposition and uses trimethoxy The amine-modified TiO of silylalkyl2The dye/M/N-TiO that electro-conductive glass is formed2Photocathode, or dye sensitization, transition metal are sunk The TiO that long-pending and trimethoxy silylalkyl amine and benzaldehyde are modified jointly2The dye/M/B-TiO of electro-conductive glass2Photocathode, Or refer to dye sensitization, transition metal deposition and TiO that trimethoxy silylalkyl amine and salicylide are modified jointly2It is conductive The dye/M/S-TiO of glass2Photocathode.
In a kind of one embodiment of method that ethanol is prepared by carbon dioxide and water of the present invention, light anode and time The voltage of interpolar is 0.4 ~ 1.0V, and electrolyte is 0.1 ~ 0.3M KHCO3Or NaHCO3The aqueous solution, the sensitization agent concentration added For 1 ~ 3 mM, sensitizer used can be any one in following substances：Fluorescein, Nile red, eosin, brave red, sieve Red bright B, fluorescence green, methylene blue, methyl orange, basic fuchsin, phloxine, phenol red, bromocresol purple, phenolphthalein, methyl red, bromine Cresols is green, bromthymol blue.
The present invention a kind of photocathode preparation method used in the method for ethanol that prepared by carbon dioxide and water be：
1) will purchase or homemade TiO2Glass electrode is soaked in the trimethoxy silylalkyl amine containing volume ratio 5% In ethanol solution, it is then heated to 60 degree and is kept for 1 hour, it is stand-by after taking-up vacuum drying, or by the electrode through pre-treatment again Immerse in the ethanol solution of the volume ratio 5% of benzaldehyde or salicylic aldehyde 1 hour, take out, front three stand-by after vacuum drying, described Epoxide silylalkyl amine molecule formula Me3OSi(CH2)nNH2Middle n=1 ~ 4；
2) using the electrode that step 1 is prepared as working electrode, treated by the use of Pt electrodes as to electrode progress electro-deposition The dye/M/N-TiO of sensitized treatment2Or dye/M/B-TiO2Or dye/M/S-TiO2Photocathode, electroplate liquid used is transition group The electroplate liquid of metal；
3）The photocathode for treating sensitized treatment that step 2 is obtained is soaked in the aqueous solution that concentration is 1 ~ 3 mM sensitizers and carried out Sensitized treatment, obtain dye/M/N-TiO2Or dye/M/B-TiO2Or dye/M/S-TiO2Photocathode, sensitizer used is glimmering Light Huang, Nile red, eosin, brave red, rhodamine B, fluorescence green, methylene blue, methyl orange, basic fuchsin, phloxine, phenol Any of red, bromocresol purple, phenolphthalein, methyl red, bromocresol green or bromthymol blue.
In photocathode preparation method embodiment of the present invention, used electro-deposition electroplate liquid is FeSO4、CoOAc2、 Ni(NO3)2、Cu(NO3)2、ZnSO4、AgNO3、HAuCl4、PdCl2、RuCl3、RhCl3Or K2PtCl6The aqueous solution.Preferable electricity The concentration of deposition electroplate liquid is 0.1M, pH=5.
The present invention's prepares the device that the method for ethanol uses by carbon dioxide and water and includes：It is close made of light transmissive material Close container, the gas conduit inside and outside connection closed container and for importing and derived device, being arranged at the liquid in container Photocathode and light anode in closed container and the power supply electrically connected with photocathode and light anode.
In the embodiment that the device that the method for ethanol uses is prepared by carbon dioxide and water of the present invention, used power supply For solar cell.All devices are completely exposed under daylight.
Further, it is of the invention to be prepared by carbon dioxide and water in the device that the method for ethanol uses, connect closed container Inside and outside gas conduit is made up of the gas conduit and pressure-equalizing pipe that carbon dioxide is filled with into closed container, in gas Be respectively arranged with valve on conduit and pressure-equalizing pipe, for by container liquid import and derived device including pump and with The liquid conduits that pump is connected with container intracavity, and the valve being arranged on liquid conduits.
The present invention by carbon dioxide and water prepare the device that the method for ethanol uses one embodiment be connect it is closed Gas conduit inside and outside container and for importing the liquid in container and derived device by conduit and balance pipe and is arranged at Supravasal pump and it is respectively arranged at pressure-equalizing pipe and supravasal valve and forms.
The method of the present invention directly can obtain ethanol under illumination condition by water and carbon dioxide, and in whole system Living resources are not needed during standby, HTHP need not be more provided, are a kind of greens completely, it is pollution-free, without natural money The ethanol preparation method of source consumption.The electrolyte obtained in the preparation method of the present invention is free of formic acid, acetic acid and methanol, its product The materials such as hydrogen and methane are not contained after testing, and the progress rectifying of obtained electrolyte is obtained into 75% ethanol water.As passed through again Further processing, can obtain the higher ethanol solution of content.
Brief description of the drawings
Accompanying drawing 1 is the proton nmr spectra of the product of embodiments of the invention 13.
Accompanying drawing 2 for the device of the present invention one embodiment schematic diagram, in Fig. 2：1 is transparent container, and 2 be the close of container Capping, 3, for electrolyte is inputted or exported into container 1 and is filled with the conduit of carbon dioxide, set what is be connected with pump thereon Valve A, valve B connection CO2Steel cylinder, 4 be power supply, and 5 be pressure-equalizing pipe, sets valve C thereon, 6 be photocathode, and 7 be light sun Pole, 8 be electrolyte.The pump for electrolyte to be inputted or exported out of container is not represented in Fig. 2.
Embodiment
The present invention explains with reference to embodiments.
First, the preparation of photocathode of the invention
1）TiO2The preparation of glass electrode：
Take commercially available TiO2The Qula that P25 powder 4.5g is scattered in PEG-20000 and 0.2g containing 0.5g leads to x-10 The 10mL aqueous solution in, with spin coating instrument coated on FTO electro-conductive glass, then sinter 1 hour in 450 C, the electricity after being handled Pole.
2）TiO2The functional modification of glass electrode：By 1）Electrode after processing prepared by step is soaked in containing 5%（V/ V）Trimethoxy silylalkyl amine（Me3OSi(CH2)nNH2, n = 1 ~ 4）Ethanol solution in, heating keep it is 60 degree 1 small When, take out electrode vacuum and dry, former electrodes are then immersed the 5% of benzaldehyde or salicylide again（V/V）1 is small in ethanol solution When, electrode is taken out again to be dried in vacuo.
3）TiO2The metal deposit of glass electrode：With through 2）Electrode after step process is made as working electrode, Pt electrodes For to electrode, with impulse method electro-deposition, electroplate liquid is respectively 0.1M, the FeSO of pH=54、CoOAc2、Ni(NO3)2、Cu (NO3)2、ZnSO4、AgNO3、HAuCl4、PdCl2、RuCl3、RhCl3Or K2PtCl6The aqueous solution.
4）TiO2The sensitization of glass electrode：Will be through 3）Electrode after step electroplating processes is soaked in the aqueous solution of sensitizer （Concentration is 1 ~ 3 mM）4 hours, photocathode is obtained, is named as dye/M/N-TiO2（Note：dye/M/N-TiO2Represent that dyestuff is quick Change, transition metal deposits and trimethoxy silylalkyl amine and benzaldehyde or the TiO of salicylide modification2Conductive glass electrode）. Sensitizer used is fluorescein, Nile red, eosin, brave red, rhodamine B, fluorescence green, methylene blue, methyl orange, alkaline product Any of red, glimmering phloxine, phenol red, bromocresol purple, phenolphthalein, methyl red, bromocresol green or bromthymol blue.
2nd, the preparation of light anode of the invention
The BiVO of the present invention4Light anode is to use document《J. A. Seabold, K. S. Choi, J. Am. Chem. Soc.2012, 134, 2186-2192.》Prepared by the method provided, both：With concentrated nitric acid by Bi (NO3)3·5H2O and VOSO4· 5H2O is dissolved as the 10mM aqueous solution respectively, after mixing, adds 2M CH3COONa regulation according to pH be 4.7, then according to 25mg/L adds H2WO4Prepare electrolyte.Worked electrode with FTO electro-conductive glass, Ag/AgCl does reference electrode, at 60 DEG C Electrolysis 900 seconds.Deionized water is washed, and 500 DEG C of Muffle furnaces are calcined 1 hour.
3rd, ethanol preparation facilities embodiment of the invention
Referring to accompanying drawing 2, the present embodiment is a transparent container 1, can also directly use a beaker of Large Copacity. One closure 2 made of polytetrafluoroethylene (PTFE) or rubber is set on transparent container 1.Closure 2 open up for set to Input or electrolyte, the pipe 3 for being filled with carbon dioxide, pressure-equalizing pipe 5 and to photocathode 6 and light anode 7 are exported in container 1 The hole of the wire of feed, while pipe 3, pipe 5 and wire are set at this some holes respectively.Valve is respectively arranged with pipe 3 and pipe 5 Door, and pipe 3 is connected with carbon dioxide source and liquid delivery pump.One power supply 4 is set outside container simultaneously, in this implementation Power supply 4 is silicon solar cell in example, and the positive pole of silicon solar cell connects light anode, and negative pole connects photocathode, has so both formed this The embodiment of one preparation facilities of invention.
The device that accompanying drawing 2 shows is positioned in photoenvironment by this device embodiment of the present invention first when in use, such as At sunshine irradiation, the valve A between tube used for bottom pouring 3 and pump, electrolyte 8 is injected in container 1 through pipe 3 by pump, then will closed Valve between pipe 3 and pump, while open the valve B on the branch pipe on the pipe 3 connected with carbon dioxide source and pressure balance Valve C on pipe 5, carbon dioxide is injected in electrolyte 8 by pipe 3, put down from the interior gas overflowed of electrolyte 8 through pressure Weighing apparatus pipe 5 empties.Close valve A, B and C.Powered by power supply to photocathode and light anode, you can second is produced in electrolyte 8 Alcohol, into electrolyte, supplement injects carbon dioxide in good time during ethanol is prepared.
4th, embodiment prepared by ethanol
Concentration of alcohol is detected with proton nmr spectra in following examples, and method sees reference document K. P. Kuhl, E. R. Cave, D. N. Abram, T. F. Jaranillo, Energy Environ. Sci. 2012, 5, 7050- 7059。
Embodiment 1
The present embodiment is with dye/Co/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.4V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.1M KHCO3Aqueous solution 25mL, add Fluorescein, concentration are 3 mM；Use CO2Air in gas displacement water, closed reactor after 30 minutes.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 5 μM×L-1。
Embodiment 2
The present embodiment is with dye/Ni/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.5V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.1M KHCO3Aqueous solution 25mL, add Fluorescence green, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 15μM×L-1。
Embodiment 3
The present embodiment is with dye/Ni/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Methylene blue, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and the silicon sun Battery connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches To 20 μM × L-1。
Embodiment 4
The present embodiment is with dye/Ni/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.8V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.3M KHCO3Aqueous solution 25mL, add Methyl orange, concentration are 2 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 18μM×L-1。
Embodiment 5
The present embodiment is with dye/Ni/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 1.0V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M NaHCO3Aqueous solution 25mL, add Basic fuchsin, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and the silicon sun Battery connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches To 22 μM × L-1。
Embodiment 6
The present embodiment is with dye/Ni/B-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Phloxine, concentration are 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and the silicon sun Battery connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches To 30 μM × L-1。
Embodiment 7
The present embodiment is with dye/Ni/S-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.8V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Nile red, concentration are 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 50μM×L-1。
Embodiment 8
The present embodiment is with dye/Ni/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 1.0V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M NaHCO3Aqueous solution 25mL, add Eosin, concentration are 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 40 μ M×L-1。
Embodiment 9
The present embodiment is with dye/Pd/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.4V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Rhodamine B, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 12μM×L-1。
Embodiment 10
The present embodiment is with dye/Pd/B-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.5V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Eosin, concentration are 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 28 μ M×L-1。
Embodiment 11
The present embodiment is with dye/Pd/S-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Eosin, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 48 μ M×L-1。
Embodiment 12
The present embodiment is with dye/Pd/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.8V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M NaHCO3Aqueous solution 25mL, add Tiger is red, and concentration is 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 13 μ M×L-1。
Embodiment 13
The present embodiment is with dye/Pt/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 1.0V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.1M KHCO3Aqueous solution 25mL, add Phenolphthalein, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 48 hours, concentration of alcohol reaches 262 μM×L-1.Heavy water is reference, dimethyl sulfoxide (DMSO)（DMSO）It is that interior target proton nmr spectra is shown in accompanying drawing with 1,3,5- phloroglucins 1。
Embodiment 14
The present embodiment is with dye/Pt/B-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.5V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.1M KHCO3Aqueous solution 25mL, add Tiger is red, and concentration is 2 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 32 μ M×L-1。
Embodiment 15
The present embodiment is with dye/Pt/S-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Bromocresol purple, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and the silicon sun Battery connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches To 46 μM × L-1。
Embodiment 16
The present embodiment is with dye/Cu/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.8V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Methyl red, concentration are 2 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 16μM×L-1。
Embodiment 17
The present embodiment is with dye/Ag/B-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Bromocresol green, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and the silicon sun Battery connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches To 24 μM × L-1。
Embodiment 18
The present embodiment is with dye/Au/S-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Bromthymol blue, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon too Positive electricity pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Repeat above procedure, after 12 hours, concentration of alcohol Reach 12 μM × L-1。
Embodiment 19
The present embodiment is with dye/Ru/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Eosin, concentration are 2 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 36 μ M×L-1。
Embodiment 20
The present embodiment is with dye/Rh/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.6V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M KHCO3Aqueous solution 25mL, add Phenol red, concentration are 3 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 44μM×L-1。
Embodiment 21
The present embodiment is with dye/Zn/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.8V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M NaHCO3Aqueous solution 25mL, add Phenol red, concentration are 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon sun electricity Pond connects, and is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 14μM×L-1。
Embodiment 22
The present embodiment is with dye/Zn/S-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.9V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M NaHCO3Aqueous solution 25mL, add Tiger is red, and concentration is 2 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 45 μ M×L-1。
Embodiment 23
The present embodiment is with dye/Fe/N-TiO2For photocathode, BiVO4Electrode is light anode, and silicon solar cell provides external electricity Power, voltage 0.8V.Electrode is installed in 50mL electrochemistry closed glass reactors, adds 0.2M NaHCO3Aqueous solution 25mL, add Eosin, concentration are 1 mM；Use CO2Air closed reactor after 30 minutes in gas displacement water.By reactor and silicon solar cell Connection, is placed under daylight, CO is supplemented again after four hours2Gas；Above procedure is repeated, after 12 hours, concentration of alcohol reaches 17 μ M×L-1。
Rectifying is carried out to the electrolyte of various embodiments above, you can obtain ethanol water.

Claims (10)

  1. A kind of 1. method that ethanol is prepared by carbon dioxide and water, it is characterised in that：The BiVO that will be adulterated with Co-P modifications and W4Electricity Light anode that pole is formed and deposited by dye sensitization, transition metal and TiO through modification2The photocathode point that electro-conductive glass is formed The KHCO containing sensitizer is not placed in3Or NaHCO3In the electrolyte that the aqueous solution is formed, and light anode and time interpolar is set to keep one Individual interval, light anode and photocathode are connected with the positive pole and negative pole of dc source respectively, titanium dioxide is filled with electrolyte Carbon gas, dc source is powered to light anode, photocathode, while make light source irradiation light anode and photocathode, keep this shape State, and the supplement carbon dioxide in good time in electrolyte, ethanol can be both generated in electrolyte, obtained electrolyte is carried out Rectifying obtains ethanol water.
  2. 2. a kind of method that ethanol is prepared by carbon dioxide and water according to claim 1, it is characterised in that quick with dyestuff TiO that change, transition metal deposit and modification2The photocathode dye sensitization of electro-conductive glass composition, transition metal deposition With with the amine-modified TiO of trimethoxy silylalkyl2The dye/M/N-TiO that electro-conductive glass is formed2Photocathode, or use dyestuff Sensitization, transition metal deposition and TiO that trimethoxy silylalkyl amine and benzaldehyde are modified jointly2The dye/M/ of electro-conductive glass B-TiO2Photocathode, or refer to dye sensitization, transition metal deposit and trimethoxy silylalkyl amine and salicylide The TiO modified jointly2The dye/M/S-TiO of electro-conductive glass2Photocathode.
  3. A kind of 3. method that ethanol is prepared by carbon dioxide and water according to claim 1 or 2, it is characterised in that：Light sun The voltage of pole and time interpolar is 0.4 ~ 1.0V, and electrolyte is 0.1 ~ 0.3M KHCO3Or NaHCO3The aqueous solution, what is added is quick Agent concentration is 1 ~ 3 mM, and sensitizer used is any one in following substances：Fluorescein, Nile red, eosin, tiger it is red, Rhodamine B, fluorescence green, methylene blue, methyl orange, basic fuchsin, phloxine, phenol red, bromocresol purple, phenolphthalein, methyl red, Bromocresol green, bromthymol blue.
  4. 4. prepared by any photocathode used in the method for ethanol that prepared by carbon dioxide and water described in claims 1 to 3 Method, it is characterised in that：
    1) will purchase or homemade TiO2Glass electrode is soaked in the ethanol of the trimethoxy silylalkyl amine containing volume ratio 5% In solution, it is then heated to 60 degree and is kept for 1 hour, it is stand-by after taking-up vacuum drying, or the electrode through pre-treatment is immersed again 1 hour in the ethanol solution of the volume ratio 5% of benzaldehyde or salicylic aldehyde, take out, trimethoxy stand-by after vacuum drying, described Silylalkyl amine molecule formula Me3OSi(CH2)nNH2Middle n=1 ~ 4；
    2) by 1）The electrode that step is prepared obtains waiting to be sensitized as working electrode by the use of Pt electrodes as to electrode progress electro-deposition The dye/M/N-TiO of processing2Or dye/M/B-TiO2Or dye/M/S-TiO2Photocathode, electroplate liquid used is magnesium-yttrium-transition metal Electroplate liquid；
    3）By 2）What step obtained treats the dye/M/N-TiO of sensitized treatment2Photocathode be soaked in concentration as 1 ~ 3 mM sensitizers The aqueous solution carries out sensitized treatment, obtains dye/M/N-TiO2Or dye/M/B-TiO2Or dye/M/S-TiO2Photocathode, it is used Sensitizer is fluorescein, Nile red, eosin, brave red, rhodamine B, fluorescence green, methylene blue, methyl orange, basic fuchsin, fluorescence Any of pink, phenol red, bromocresol purple, phenolphthalein, methyl red, bromocresol green or bromthymol blue.
  5. 5. photocathode preparation method according to claim 4, it is characterised in that electro-deposition electroplate liquid is FeSO4、CoOAc2、 Ni(NO3)2、Cu(NO3)2、ZnSO4、AgNO3、HAuCl4、PdCl2、RuCl3、RhCl3Or K2PtCl6The aqueous solution.
  6. 6. photocathode preparation method according to claim 5, it is characterised in that the concentration of electro-deposition electroplate liquid is 0.1M, pH = 5。
  7. 7. any described in claims 1 to 3 is prepared the device that the method for ethanol uses by carbon dioxide and water, it is characterised in that Including：Closed container, the gas conduit inside and outside connection closed container and for by the liquid in container made of light transmissive material Import and derived device, the photocathode that is arranged in closed container and light anode and electrically connected with photocathode and light anode Power supply.
  8. 8. according to claim 7 prepared the device that the method for ethanol uses by carbon dioxide and water, it is characterised in that institute The power supply used is solar cell.
  9. 9. according to claim 8 prepared the device that the method for ethanol uses by carbon dioxide and water, it is characterised in that even Gas conduit and pressure-equalizing pipe of the gas conduit from being filled with carbon dioxide into closed container inside and outside logical closed container Form, valve is respectively arranged with gas conduit and pressure-equalizing pipe, for the liquid in container to be imported and derived dress Put the liquid conduits being connected including pump and with pump and container intracavity, and the valve being arranged on liquid conduits.
  10. 10. according to claim 8 prepared the device that the method for ethanol uses by carbon dioxide and water, it is characterised in that even Gas conduit inside and outside logical closed container and for importing the liquid in container and derived device is by conduit and pressure balance Manage and be arranged at supravasal pump and be respectively arranged at balance pipe and supravasal valve composition.
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