CN105332002A - Method for preparing ethyl alcohol through carbon dioxide and water - Google Patents

Method for preparing ethyl alcohol through carbon dioxide and water Download PDF

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Publication number
CN105332002A
CN105332002A CN201510914432.8A CN201510914432A CN105332002A CN 105332002 A CN105332002 A CN 105332002A CN 201510914432 A CN201510914432 A CN 201510914432A CN 105332002 A CN105332002 A CN 105332002A
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photocathode
tio
dye
electrode
ethanol
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CN105332002B (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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Hybrid Cells (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention discloses a method for preparing ethyl alcohol through carbon dioxide and water, a preparation method for used relative devices and a device for the method. The method for preparing the ethyl alcohol comprises the steps that a photo-anode composed of BiVO4 and a photo-cathode composed of dye/M/N-TiO2 or dye/M/B-TiO2 or dye/M/S-TiO2 are put into an electrolyte solution composed of a sensitizing agent-containing KHCO3 or NaHCO3 aqueous solution, and a gap is maintained between the photo-anode and the photo-cathode; the photo-anode and the photo-cathode are connected to a positive electrode and a negative electrode of a direct-current power source respectively, the electrolyte solution is filled with carbon dioxide gas to make the direct-current power source electrify the photo-anode and the photo-cathode, a light source is made to illuminate the photo-anode and the photo-cathode at the same time, and the ethyl alcohol can be generated in the electrolyte solution.

Description

A kind of method being prepared ethanol by carbonic acid gas and water
Technical field
The present invention relates to related device preparation method that a kind of preparation method of ethanol and this method use and a kind of method that device, particularly carbonic acid gas and water prepare ethanol and the related device preparation method used and device.
Background technology
Ethanol is important industrial chemicals or fuel, also can be beverage simultaneously.At present, preparing ethanol has two approach, and both fermentation method was prepared or the method for ethene by catalytic hydration obtained.Fermentation method of the prior art is mainly for the production of edible ethanol or alcopop, the method needs to consume a large amount of cereal, also have and adopt stalk or other fermentation of biomaterials to prepare ethanol, CN103509828B Chinese patent that the CN1006902 Chinese patent of such as authorization on February 21 nineteen ninety and on May 20th, 2015 authorize.Ethylene hydration rule of the prior art needs High Temperature High Pressure, and its preparation condition is harsh, need consume mass energy.
Summary of the invention
The invention provides a kind of method being different from prior art completely and prepare ethanol, namely under illumination condition, directly obtain the method for highly purified aqueous ethanolic solution by water and carbonic acid gas by electrical combined catalysis high-level efficiency, the present invention provides preparation method and the device of the Primary Component involved by this method simultaneously.
A kind of method preparing ethanol by carbonic acid gas and water of the present invention is: will modify with Co-P and BiVO that W adulterates 4electrode form light anode and by dye sensitization, transition metal deposit with modified TiO 2the photocathode that conductive glass is formed is placed in the KHCO containing sensitizing agent respectively 3or NaHCO 3in the electrolytic solution that the aqueous solution is formed, and make to keep an interval between light anode and photocathode, light anode is connected with negative pole with the positive pole of direct supply respectively with photocathode, in electrolytic solution, be filled with carbon dioxide, direct supply powered to light anode, photocathode, makes light source irradiation light anode and photocathode simultaneously, keep this state, and supplement carbon dioxide in electrolytic solution in good time, both can generate ethanol in electrolytic solution, and the electrolytic solution obtained be carried out rectifying and obtains aqueous ethanolic solution.
Of the present inventionly a kind ofly prepared in the embodiment of the method for ethanol by carbonic acid gas and water, deposited by dye sensitization, transition metal with the TiO modified 2the photocathode that conductive glass is formed is dye sensitization, transition metal deposition and with the amine-modified TiO of trimethoxy silylalkyl 2the dye/M/N-TiO that conductive glass is formed 2photocathode, or dye sensitization, transition metal deposition the TiO jointly modified with trimethoxy silylalkyl amine and phenyl aldehyde 2the dye/M/B-TiO of conductive glass 2photocathode, or refer to the TiO jointly modified with trimethoxy silylalkyl amine and salicylic aldehyde of dye sensitization, transition metal deposition 2the dye/M/S-TiO of conductive glass 2photocathode.
A kind ofly prepared in an embodiment of the method for ethanol by carbonic acid gas and water of the present invention, the voltage between light anode and photocathode is 0.4 ~ 1.0V, and electrolytic solution is the KHCO of 0.1 ~ 0.3M 3or NaHCO 3the aqueous solution, the sensitizing agent concentration added is 1 ~ 3mM, and sensitizing agent used can be any one in following substances: fluorescent yellow, Nile red, eosin, tiger are red, rhodamine B, fluorescence green, methylene blue, tropeolin-D, magenta, phloxine, phenolsulfonphthalein, purpurum bromocresolis, phenolphthalein, methyl red, tetrabromo-mcresolsulfonphthalein, dibromothymolsulfonphthalein.
Of the present inventionly a kind ofly prepare by carbonic acid gas and water the photocathode preparation method used in the method for ethanol and be:
1) will to buy or homemade TiO 2glass electrode is soaked in the ethanolic soln of the trimethoxy silylalkyl amine containing volume ratio 5%, then be heated to 60 degree and keep 1 hour, stand-by after taking out vacuum-drying, or the electrode through pre-treatment to be immersed again in the ethanolic soln of the volume ratio 5% of phenyl aldehyde or salicylic aldehyde 1 hour, take out, stand-by after vacuum-drying, described trimethoxy silylalkyl amine molecule formula Me 3oSi (CH 2) nnH 2middle n=1 ~ 4;
2) electrode step 1 prepared, as working electrode, carries out as to electrode the dye/M/N-TiO that galvanic deposit obtains treating sensitized treatment with Pt electrode 2or dye/M/B-TiO 2or dye/M/S-TiO 2photocathode, electroplate liquid used is the electroplate liquid of magnesium-yttrium-transition metal;
3) step 2 is obtained to treat that the photocathode of sensitized treatment is soaked in concentration be that the aqueous solution of 1 ~ 3mM sensitizing agent carries out sensitized treatment, obtain dye/M/N-TiO 2or dye/M/B-TiO 2or dye/M/S-TiO 2photocathode, sensitizing agent used is any one in fluorescent yellow, Nile red, eosin, red, the rhodamine B of tiger, fluorescence green, methylene blue, tropeolin-D, magenta, phloxine, phenolsulfonphthalein, purpurum bromocresolis, phenolphthalein, methyl red, tetrabromo-mcresolsulfonphthalein or dibromothymolsulfonphthalein.
In photocathode preparation method embodiment of the present invention, the galvanic deposit electroplate liquid used is FeSO 4, CoOAc 2, Ni (NO 3) 2, Cu (NO 3) 2, ZnSO 4, AgNO 3, HAuCl 4, PdCl 2, RuCl 3, RhCl 3or K 2ptCl 6the aqueous solution.The concentration of preferred galvanic deposit electroplate liquid is 0.1M, pH=5.
The device that the method preparing ethanol by carbonic acid gas and water of the present invention uses comprises: the encloses container made with light transmissive material, is communicated with gas duct inside and outside encloses container and for being imported by the liquid in container and the device of derivation, the power supply that is arranged at photocathode in encloses container and light anode and is electrically connected with photocathode and light anode.
In the embodiment of the device that the method preparing ethanol by carbonic acid gas and water of the present invention uses, the power supply used is solar cell.Under all devices are exposed to daylight completely.
Further, in the device that the method preparing ethanol by carbonic acid gas and water of the present invention uses, the gas duct be communicated with inside and outside encloses container is made up of the gas duct and pressure equalizing pipe being filled with carbon dioxide in encloses container, gas duct and pressure equalizing pipe are respectively arranged with valve, for the liquid in container being imported the fluid conduits comprising pump with the device of deriving and be connected with container intracavity with pump, and be arranged at the valve on fluid conduits.
The embodiment of device that the method preparing ethanol by carbonic acid gas and water of the present invention uses be is communicated with gas duct inside and outside encloses container and for the liquid in container is imported and the device of derivation by conduit and equilibration tube and be arranged at supravasal pump and be arranged at pressure equalizing pipe respectively and supravasal valve is formed.
Method of the present invention directly can obtain ethanol by water and carbonic acid gas under illumination condition, and namely Biological resources are not needed in whole preparation process, more do not need to provide High Temperature High Pressure, be a kind of completely green, pollution-free, without the ethanol preparation method of the comsumption of natural resources.The electrolytic solution obtained in preparation method of the present invention is not containing formic acid, acetic acid and methyl alcohol, and the electrolytic solution obtained not containing the material such as hydrogen and methane, is carried out the aqueous ethanolic solution that rectifying obtains 75% by its product after testing.As again through process further, the ethanolic soln that content is higher can be obtained.
Accompanying drawing explanation
Accompanying drawing 1 is the proton nmr spectra of embodiments of the invention 13 product.
Accompanying drawing 2 is an embodiment schematic diagram of device of the present invention, in Fig. 2: 1 is transparent container, 2 is the sealing cover of container, and 3 is the conduit inputing or outputing electrolytic solution He be filled with carbon dioxide in container 1, it is arranged the valve A be connected with pump, valve B connects CO 2steel cylinder, 4 is power supply, and 5 is pressure equalizing pipe, it is arranged valve C, and 6 is photocathode, and 7 is light anode, and 8 is electrolytic solution.Do not indicate in Fig. 2 for input in container or the pump of deriving electrolytic solution.
Embodiment
The present invention is below in conjunction with embodiment explanation.
One, the preparation of photocathode of the present invention
1) TiO 2the preparation of glass electrode:
Get the TiO that business is bought 2p25 powder 4.5g is scattered in the 10mL aqueous solution of the Triton x-10 of PEG-20000 and 0.2g containing 0.5g, is coated on FTO conductive glass with spin coating instrument, then sinters 1 hour at 450 C, obtains the electrode after processing.
2) TiO 2the functional modification of glass electrode: by 1) electrode after the process prepared of step is soaked in containing 5%(V/V) trimethoxy silylalkyl amine (Me 3oSi (CH 2) nnH 2, n=1 ~ 4) ethanolic soln in, heating maintenance 60 degree 1 hour, takes out electrode vacuum dry, and then former electrodes is immersed the 5%(V/V of phenyl aldehyde or salicylic aldehyde) in ethanolic soln 1 hour, again take out electrode and carry out vacuum-drying.
3) TiO 2the metal deposition of glass electrode: using through 2) electrode after step process is as working electrode, and Pt electrode is as to electrode, and use impulse method galvanic deposit, electroplate liquid is respectively 0.1M, the FeSO of pH=5 4, CoOAc 2, Ni (NO 3) 2, Cu (NO 3) 2, ZnSO 4, AgNO 3, HAuCl 4, PdCl 2, RuCl 3, RhCl 3or K 2ptCl 6the aqueous solution.
4) TiO 2the sensitization of glass electrode: by through 3) electrode after step electroplating processes to be soaked in the aqueous solution of sensitizing agent (concentration is 1 ~ 3mM) 4 hours, obtains photocathode, called after dye/M/N-TiO 2(note: dye/M/N-TiO 2represent the TiO that dye sensitization, transition metal deposition and trimethoxy silylalkyl amine and phenyl aldehyde or salicylic aldehyde are modified 2conductive glass electrode).Sensitizing agent used is any one in fluorescent yellow, Nile red, eosin, red, the rhodamine B of tiger, fluorescence green, methylene blue, tropeolin-D, magenta, glimmering phloxine, phenolsulfonphthalein, purpurum bromocresolis, phenolphthalein, methyl red, tetrabromo-mcresolsulfonphthalein or dibromothymolsulfonphthalein.
Two, the preparation of smooth anode of the present invention
BiVO of the present invention 4light anode be adopt document " J.A.Seabold, K.S.Choi, j.Am.Chem.Soc. 2012, 134, 2186-2192. " provide method preparation, both: with concentrated nitric acid by Bi (NO 3) 35H 2o and VOSO 45H 2o is dissolved as the aqueous solution of 10mM respectively, after mixing, adds 2MCH 3it is 4.7 that COONa regulates according to pH, then adds H according to 25mg/L 2wO 4prepare electrolytic solution.To work electrode with FTO conductive glass, Ag/AgCl does reference electrode, electrolysis 900 seconds at 60 DEG C.Deionized water wash, 500 DEG C of retort furnaces calcine 1 hour.
Three, ethanol preparation facilities embodiment of the present invention
See accompanying drawing 2, the present embodiment is a transparent container 1, also directly can use a jumbo beaker.Transparent container 1 arranges a sealing cover 2 made with tetrafluoroethylene or rubber.Sealing cover 2 offer for input is set in container 1 or derive electrolytic solution, be filled with the pipe 3 of carbon dioxide, the hole of pressure equalizing pipe 5 and the wire to photocathode 6 and light anode 7 feed, respectively pipe 3, pipe 5 and wire are set at this some holes place simultaneously.Pipe 3 and pipe 5 are respectively arranged with valve, and pipe 3 is connected with liquid delivery pump with carbon dioxide gas body source.Outside container, arrange a power supply 4, power supply 4 is silicon solar cell in the present embodiment, and the positive pole of silicon solar cell connects light anode, and negative pole connects photocathode, has so both formed the embodiment of a preparation facilities of the present invention simultaneously.
First the device that accompanying drawing 2 shows is positioned in photoenvironment by this device embodiment of the present invention in use, as solar light irradiation place, valve A between tube used for bottom pouring 3 and pump, through pipe 3, electrolytic solution 8 is injected in container 1 by pump, then by the valve between blanked-off pipe 3 and pump, open the valve B on the arm on the pipe 3 be communicated with carbon dioxide gas body source and the valve C on pressure equalizing pipe 5 simultaneously, inject in electrolytic solution 8 by pipe 3 by carbon dioxide, the gas overflowed in electrolytic solution 8 is emptying through pressure equalizing pipe 5.Valve-off A, B and C.By power supply to photocathode and light anode supply, ethanol can be produced in electrolytic solution 8, in the process preparing ethanol, in electrolytic solution, supplement injecting carbon dioxide gas in good time.
Four, the embodiment prepared of ethanol
In following examples, alcohol concn proton nmr spectra detects, and method sees reference document K.P.Kuhl, E.R.Cave, D.N.Abram, T.F.Jaranillo, energyEnviron.Sci. 2012, 5, 7050-7059.
Embodiment 1
The present embodiment is with dye/Co/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.4V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.1MKHCO 3aqueous solution 25mL, adds fluorescent yellow, and concentration is 3mM; Use CO 2air in gas displacement water, closed reactor after 30 minutes.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 5 μMs × L -1.
Embodiment 2
The present embodiment is with dye/Ni/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.5V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.1MKHCO 3aqueous solution 25mL, adds fluorescence green, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 15 μMs × L -1.
Embodiment 3
The present embodiment is with dye/Ni/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds methylene blue, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 20 μMs × L -1.
Embodiment 4
The present embodiment is with dye/Ni/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.8V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.3MKHCO 3aqueous solution 25mL, adds tropeolin-D, and concentration is 2mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 18 μMs × L -1.
Embodiment 5
The present embodiment is with dye/Ni/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 1.0V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MNaHCO 3aqueous solution 25mL, adds magenta, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 22 μMs × L -1.
Embodiment 6
The present embodiment is with dye/Ni/B-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds phloxine, and concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 30 μMs × L -1.
Embodiment 7
The present embodiment is with dye/Ni/S-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.8V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds Nile red, and concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 50 μMs × L -1.
Embodiment 8
The present embodiment is with dye/Ni/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 1.0V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MNaHCO 3aqueous solution 25mL, adds eosin, and concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 40 μMs × L -1.
Embodiment 9
The present embodiment is with dye/Pd/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.4V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds rhodamine B, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 12 μMs × L -1.
Embodiment 10
The present embodiment is with dye/Pd/B-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.5V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds eosin, and concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 28 μMs × L -1.
Embodiment 11
The present embodiment is with dye/Pd/S-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds eosin, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 48 μMs × L -1.
Embodiment 12
The present embodiment is with dye/Pd/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.8V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MNaHCO 3aqueous solution 25mL, add brave red, concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 13 μMs × L -1.
Embodiment 13
The present embodiment is with dye/Pt/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 1.0V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.1MKHCO 3aqueous solution 25mL, adds phenolphthalein, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 48 hours, alcohol concn reaches 262 μMs × L -1.Heavy water is reference, and dimethyl sulfoxide (DMSO) (DMSO) and 1,3,5-Phloroglucinol are that interior target proton nmr spectra is shown in accompanying drawing 1.
Embodiment 14
The present embodiment is with dye/Pt/B-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.5V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.1MKHCO 3aqueous solution 25mL, add brave red, concentration is 2mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 32 μMs × L -1.
Embodiment 15
The present embodiment is with dye/Pt/S-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds purpurum bromocresolis, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 46 μMs × L -1.
Embodiment 16
The present embodiment is with dye/Cu/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.8V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds methyl red, and concentration is 2mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 16 μMs × L -1.
Embodiment 17
The present embodiment is with dye/Ag/B-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds tetrabromo-mcresolsulfonphthalein, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 24 μMs × L -1.
Embodiment 18
The present embodiment is with dye/Au/S-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds dibromothymolsulfonphthalein, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 12 μMs × L -1.
Embodiment 19
The present embodiment is with dye/Ru/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds eosin, and concentration is 2mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 36 μMs × L -1.
Embodiment 20
The present embodiment is with dye/Rh/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.6V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MKHCO 3aqueous solution 25mL, adds phenolsulfonphthalein, and concentration is 3mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 44 μMs × L -1.
Embodiment 21
The present embodiment is with dye/Zn/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.8V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MNaHCO 3aqueous solution 25mL, adds phenolsulfonphthalein, and concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 14 μMs × L -1.
Embodiment 22
The present embodiment is with dye/Zn/S-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.9V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MNaHCO 3aqueous solution 25mL, add brave red, concentration is 2mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 45 μMs × L -1.
Embodiment 23
The present embodiment is with dye/Fe/N-TiO 2for photocathode, BiVO 4electrode is light anode, and silicon solar cell provides external electric power, voltage 0.8V.Installing electrodes in 50mL electrochemistry closed glass reactor, adds 0.2MNaHCO 3aqueous solution 25mL, adds eosin, and concentration is 1mM; Use CO 2air closed reactor after 30 minutes in gas displacement water.Reactor is connected with silicon solar cell, under being placed in daylight, after four hours, again supplements CO 2gas; Repeat above process, after 12 hours, alcohol concn reaches 17 μMs × L -1.
Rectifying is carried out to the electrolytic solution of above each embodiment, can aqueous ethanolic solution be obtained.

Claims (10)

1. prepared a method for ethanol by carbonic acid gas and water, it is characterized in that: by the BiVO modified with Co-P and W adulterates 4electrode form light anode and by dye sensitization, transition metal deposit with modified TiO 2the photocathode that conductive glass is formed is placed in the KHCO containing sensitizing agent respectively 3or NaHCO 3in the electrolytic solution that the aqueous solution is formed, and make to keep an interval between light anode and photocathode, light anode is connected with negative pole with the positive pole of direct supply respectively with photocathode, in electrolytic solution, be filled with carbon dioxide, direct supply powered to light anode, photocathode, makes light source irradiation light anode and photocathode simultaneously, keep this state, and supplement carbon dioxide in electrolytic solution in good time, both can generate ethanol in electrolytic solution, and the electrolytic solution obtained be carried out rectifying and obtains aqueous ethanolic solution.
2. a kind of method being prepared ethanol by carbonic acid gas and water according to claim 1, it is characterized in that by dye sensitization, transition metal deposit with modify TiO 2the photocathode that conductive glass is formed is dye sensitization, transition metal deposition and with the amine-modified TiO of trimethoxy silylalkyl 2the dye/M/N-TiO that conductive glass is formed 2photocathode, or dye sensitization, transition metal deposition the TiO jointly modified with trimethoxy silylalkyl amine and phenyl aldehyde 2the dye/M/B-TiO of conductive glass 2photocathode, or refer to the TiO jointly modified with trimethoxy silylalkyl amine and salicylic aldehyde of dye sensitization, transition metal deposition 2the dye/M/S-TiO of conductive glass 2photocathode.
3. a kind of method being prepared ethanol by carbonic acid gas and water according to claim 1 and 2, it is characterized in that: the voltage between light anode and photocathode is 0.4 ~ 1.0V, electrolytic solution is the KHCO of 0.1 ~ 0.3M 3or NaHCO 3the aqueous solution, the sensitizing agent concentration added is 1 ~ 3mM, and sensitizing agent used can be any one in following substances: fluorescent yellow, Nile red, eosin, tiger are red, rhodamine B, fluorescence green, methylene blue, tropeolin-D, magenta, phloxine, phenolsulfonphthalein, purpurum bromocresolis, phenolphthalein, methyl red, tetrabromo-mcresolsulfonphthalein, dibromothymolsulfonphthalein.
4. any one described in claims 1 to 3 is prepared the photocathode preparation method used in the method for ethanol by carbonic acid gas and water, it is characterized in that:
1) will to buy or homemade TiO 2glass electrode is soaked in the ethanolic soln of the trimethoxy silylalkyl amine containing volume ratio 5%, then be heated to 60 degree and keep 1 hour, stand-by after taking out vacuum-drying, or the electrode through pre-treatment to be immersed again in the ethanolic soln of the volume ratio 5% of phenyl aldehyde or salicylic aldehyde 1 hour, take out, stand-by after vacuum-drying, described trimethoxy silylalkyl amine molecule formula Me 3oSi (CH 2) nnH 2middle n=1 ~ 4;
2) using 1) electrode prepared of step as working electrode, carry out as to electrode the dye/M/N-TiO that galvanic deposit obtains treating sensitized treatment with Pt electrode 2or dye/M/B-TiO 2or dye/M/S-TiO 2photocathode, electroplate liquid used is the electroplate liquid of magnesium-yttrium-transition metal;
3) by 2) dye/M/N-TiO treating sensitized treatment that obtains of step 2photocathode to be soaked in concentration be that the aqueous solution of 1 ~ 3mM sensitizing agent carries out sensitized treatment, obtain dye/M/N-TiO 2or dye/M/B-TiO 2or dye/M/S-TiO 2photocathode, sensitizing agent used is any one in fluorescent yellow, Nile red, eosin, red, the rhodamine B of tiger, fluorescence green, methylene blue, tropeolin-D, magenta, phloxine, phenolsulfonphthalein, purpurum bromocresolis, phenolphthalein, methyl red, tetrabromo-mcresolsulfonphthalein or dibromothymolsulfonphthalein.
5. photocathode preparation method according to claim 4, is characterized in that galvanic deposit electroplate liquid is FeSO 4, CoOAc 2, Ni (NO 3) 2, Cu (NO 3) 2, ZnSO 4, AgNO 3, HAuCl 4, PdCl 2, RuCl 3, RhCl 3or K 2ptCl 6the aqueous solution.
6. photocathode preparation method according to claim 5, is characterized in that the concentration of galvanic deposit electroplate liquid is 0.1M, pH=5.
7. the device that the arbitrary method preparing ethanol by carbonic acid gas and water described in claims 1 to 3 uses, is characterized in that comprising: the encloses container made with light transmissive material, be communicated with gas duct inside and outside encloses container and for the device being imported by the liquid in container and derive, the power supply being arranged at photocathode in encloses container and light anode and being electrically connected with photocathode and light anode.
8. the device being prepared the method use of ethanol by carbonic acid gas and water according to claim 7, is characterized in that used power supply is for solar cell.
9. the device being prepared the method use of ethanol by carbonic acid gas and water according to claim 8, it is characterized in that the gas duct be communicated with inside and outside encloses container is made up of the gas duct and pressure equalizing pipe being filled with carbon dioxide in encloses container, gas duct and pressure equalizing pipe are respectively arranged with valve, for the liquid in container being imported the fluid conduits comprising pump with the device of deriving and be connected with container intracavity with pump, and be arranged at the valve on fluid conduits.
10. the device that uses of the method preparing ethanol by carbonic acid gas and water according to claim 8, it is characterized in that being communicated with gas duct inside and outside encloses container and for the device that the liquid in container imported and derives by conduit and pressure equalizing pipe and be arranged at supravasal pump and be arranged at equilibration tube respectively and supravasal valve is formed.
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