CN110079816A - A kind of device and method of photoelectrocatalysis fixed nitrogen synthesis ammonia - Google Patents
A kind of device and method of photoelectrocatalysis fixed nitrogen synthesis ammonia Download PDFInfo
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- CN110079816A CN110079816A CN201910359843.3A CN201910359843A CN110079816A CN 110079816 A CN110079816 A CN 110079816A CN 201910359843 A CN201910359843 A CN 201910359843A CN 110079816 A CN110079816 A CN 110079816A
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- exchange membrane
- cation
- fixed nitrogen
- anion
- film
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 281
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 140
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 138
- 238000005341 cation exchange Methods 0.000 claims abstract description 105
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 238000009434 installation Methods 0.000 claims abstract description 22
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 14
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 11
- 230000005684 electric field Effects 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 41
- 238000005349 anion exchange Methods 0.000 claims description 35
- 229920002492 poly(sulfone) Polymers 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 229920000557 Nafion® Polymers 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- -1 polyethylene benzyl chloride Polymers 0.000 claims description 11
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 10
- 229920000128 polypyrrole Polymers 0.000 claims description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 125000001302 tertiary amino group Chemical group 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 238000010345 tape casting Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 6
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 5
- 239000010985 leather Substances 0.000 claims description 5
- 239000011943 nanocatalyst Substances 0.000 claims description 5
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 3
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001661 Chitosan Polymers 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002115 Sodium cellulose phosphate Polymers 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one 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
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of device and methods of photoelectrocatalysis fixed nitrogen synthesis ammonia, it is related to electro-catalysis electrolysis tech field, a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation, it includes that anode chamber and cathode chamber are divided into two-compartment cell by the photoelectric compound film that Bipolar Membrane and nanometer fixed nitrogen catalytic membrane form, the Bipolar Membrane includes anion-exchange membrane and cation-exchange membrane, nanometer fixed nitrogen catalyst film is carried on cation-exchange membrane surface, electrolyte aqueous solution is added in anode chamber, cathode chamber is full of nitrogen, using BiVO4 or Pt electrode as anode, fixed nitrogen catalyst film is as cathode, the container for filling dilute sulfuric acid is arranged in cathode chamber, for absorbing the ammonia of generation, using xenon lamp as light source, external dc power supply provides electric field action power, the anode of DC power supply, cathode is connect with anode and cathode respectively；The present invention carries out photoelectrocatalysis fixed nitrogen in non-aqueous solution, the beneficial effect for having the generation for effectively inhibiting liberation of hydrogen side reaction, promoting photoelectrocatalysis nitrogen-fixing efficiency.
Description
Technical field
The present invention relates to photoelectrocatalysis electrolysis tech fields, and in particular to a kind of device of photoelectrocatalysis fixed nitrogen synthesis ammonia and
Method.
Background technique
Nitrogen molecular is a kind of simple substance that stability is high, thirdly key bond energy is 94l KJ.mol-1, inertia is big, not easily-activated.
It is N that fixed nitrogen, which synthesizes ammonia,2The process gradually combined with light induced electron and proton, there are serious liberations of hydrogen in fixed nitrogen reaction process
Competitive reaction causes ammonia synthesis efficiency to significantly reduce.It is largely concentrated in relation to improving the research of photoelectrocatalysis nitrogen-fixing efficiency at present
In the research to catalyst itself, such as regulate and control catalyst particle size, activated adoption site, changes electron transport route, interface element
Electron density distribution etc..For these methods although achieving some effects to a certain extent, efficiency is still relatively low.
In usually used single chamber or dual chamber fixed nitrogen system containing diaphragm, proton is generally mentioned by neutral or acidic electrolysis bath
For making H due to the generation of fixed nitrogen reaction and liberation of hydrogen side reaction+Concentration is in continuous variable condition, causes catalyst that cannot stablize
It plays a role.Consider from aerodynamic point, H+It is to participate in ammonia synthesis reaction raw material, increases its concentration and peomote reaction；But
The H of high concentration+It is more advantageous to the generation for leading to liberation of hydrogen side reaction, ammonia synthesis efficiency is caused to decline.Therefore, how to effectively control H+
Delivery rate, and be able to maintain that stable H+Concentration is the significant challenge that ammino architectonical faces.
Summary of the invention
For the problem that photoelectrocatalysis nitrogen-fixing efficiency is low in the prior art, and there are serious liberation of hydrogen side reaction, the present invention
A kind of method for being intended to provide photoelectrocatalysis fixed nitrogen synthesis ammonia, not only improves photoelectrocatalysis nitrogen-fixing efficiency, but also can effectively reduce
Liberation of hydrogen side reaction.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation comprising answered by the photoelectricity that Bipolar Membrane and nanometer fixed nitrogen catalytic membrane form
It closes film and anode chamber and cathode chamber is divided into two-compartment cell, the Bipolar Membrane includes anion-exchange membrane and cation-exchange membrane,
Nanometer fixed nitrogen catalyst film is carried on cation-exchange membrane surface, and electrolyte aqueous solution is added in anode chamber, and cathode chamber is full of nitrogen
Gas, with BiVO4Or Pt electrode, as anode, the container for filling dilute sulfuric acid is arranged as cathode, cathode chamber in fixed nitrogen catalyst film,
For absorbing the ammonia of generation, using xenon lamp as light source, external dc power supply provides electric field action power, and DC power supply is just
Pole, cathode are connect with anode and cathode respectively.Under electric field action, water decomposition, the H of generation occur for the intermediate layer of Bipolar Membrane+Ion enters cathode chamber through cation-exchange membrane and participates in reduction reaction, OH-Ion enters anode chamber through anion-exchange membrane
Oxidation reaction occurs, Bipolar Membrane is able to maintain that the stabilization of yin, yang pole room pH.
Further, the photoelectric compound film the preparation method is as follows:
(1) anion-exchange membrane is prepared: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion
Support rib of the mixture of one or more of exchanger resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane
Frame, primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as anion-exchange membrane
Fixed group prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, with a thickness of 30~80 μm；
(2) it prepares cation-exchange membrane: being appointed using one or more of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene
Support frame of the mixture of meaning ratio as cation-exchange membrane, one or more of sulfonic group, carboxylic acid group and phosphate
Fixed group of the mixture of arbitrary proportion as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step (1)
The anion exchange film surface of preparation, obtains cation-exchange membrane, with a thickness of 30~80 μm；
(3) it prepares nanometer fixed nitrogen catalyst film: being loaded nanometer fixed nitrogen catalyst fines using spin-coating method or spray coating method
In cation-exchange membrane surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm.
Still further, (1) prepares anion-exchange membrane in the preparation method of the photoelectric compound film: using polyethylene
One or more of alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion exchange resin, polyethylene benzyl chloride are appointed
Support frame of the mixture of meaning ratio as anion-exchange membrane, primary amino group, secondary amino group, tertiary amino, one kind of quaternary ammonium or
Fixed group of the mixture of several arbitrary proportions as anion-exchange membrane prepares anion exchange film liquid and passes through the tape casting
Anion-exchange membrane is prepared, with a thickness of 30~80 μm；Method particularly includes:
It will be mixed scattered as the substance of anion-exchange membrane support frame and the substance as anion-exchange membrane fixed group
In container, the aqueous acetic acid that mass fraction is 0.05%~0.2% is added, 60 DEG C of dissolutions are heated under stirring, to complete
Deaeration in 2 hours is stood after dissolution and forms anion exchange film liquid, is then cast and is done on clean band frame glass plate in smooth, uses
The glutaraldehyde water solution that mass fraction is 5~10% is crosslinked, and volume is the 1/6 of anion exchange film liquid, in 60 DEG C of drum
It is dried in wind drying box, obtains anion-exchange membrane.
Still further, (2) prepare cation-exchange membrane in the preparation method of the photoelectric compound film: using polyethylene
Support rib of the mixture of one or more of alcohol, polyphenylene oxide, polysulfones and styrene arbitrary proportion as cation-exchange membrane
Frame, fixation of the mixture of one or more of sulfonic group, carboxylic acid group and phosphate arbitrary proportion as cation-exchange membrane
Group prepares cation-exchange membrane liquid and is cast the anion exchange film surface prepared in step (1), obtains cationic exchange
Film, with a thickness of 30~80 μm；Method particularly includes:
It will be mixed scattered as the substance of cation-exchange membrane support frame and the substance as cation-exchange membrane fixed group
In container, the phosphate aqueous solution that mass fraction is 0.05%~0.1% is added, 60 DEG C of dissolutions are heated under stirring, to complete
Deaeration in 2 hours is stood after dissolution and forms cation-exchange membrane liquid, is then cast the anion-exchange membrane table prepared in step (1)
Face, use mass fraction for 5~10% FeCl3Aqueous solution is crosslinked, and volume is the 1/6 of cation-exchange membrane liquid, dry
After obtain cation-exchange membrane.
Still further, (3) prepare nanometer fixed nitrogen catalyst film in the preparation method of the photoelectric compound film: using
Nanometer fixed nitrogen catalyst fines are carried on cation-exchange membrane surface by spin-coating method or spray coating method, and nanometer fixed nitrogen catalyst film is thick
Degree is 0.1~2.0 μm；Method particularly includes:
It disperses nano-catalyst particles in Nafion solution, selects the cation-exchange membrane table prepared in step (2)
Face is in leather hard, when surface also has viscosity, the Nafion solution of nanometer fixed nitrogen catalyst granules is sprayed or is spun on
Cation-exchange membrane surface, cation-exchange membrane surface has viscosity at this time, can securely fix nano particle.Utilize sun
Ion exchange film liquid has sticking feature before not being completely dried, by nanometer fixed nitrogen catalyst be uniformly securely carried on sun from
Proton exchange surface effectively avoids nanocatalyst that agglomeration occurs.
Still further, the nanometer fixed nitrogen catalyst film includes BiOCl, BiOBr, g-C3N4、Fe、Co、Ni、Ru、
The mixing of one of Mg-Al, Ni-Fe, Zn-Cr or Zn-Al layered double hydroxide or two or more arbitrary proportions
Object.
Still further, the photoelectric compound film has light transmission, light transmittance is 30%~76.4%.The photoelectricity is multiple
Closing film has good optical clarity, is conducive to fully absorbing for photon.
A kind of fixed nitrogen synthesis ammonia method using photoelectrocatalysis fixed nitrogen synthetic ammonia installation, is that electrolyte water is added in anode chamber
Solution, cathode chamber is full of nitrogen, with BiVO4Or Pt electrode is connect as anode and with the anode of DC power supply, fixed nitrogen catalyst
Film is connect as cathode and with the cathode of DC power supply, and it is 0.1~1.0mol L that cathode chamber setting, which fills concentration,-1Dilute sulfuric acid
Container, for absorbing the ammonia of generation, using xenon lamp as light source, the voltage of external dc power supply is 0.5~2.0V.Water decomposition
Rate can be controlled by adjusting the voltage of external dc power supply, make H+Generating rate and nitrogen reduction reaction wear rate
Match, it is 0.5~2.0V that the present invention, which selects voltage, that is, can reach H+The purpose of ion " produce and disappear ".
Further, the electrolyte aqueous solution is Na2SO4, NaOH and KOH aqueous solution, the electrolyte are water-soluble
Liquid concentration is 0.10~2.0mol L-1。
Still further, the BiVO4Or it is connected in Pt electrode insertion anode chamber's electrolyte with positive pole and oxygen occurs
Change reaction, nanometer fixed nitrogen catalyst film, which is connected as cathode with power cathode, occurs nitrogen reduction reaction, closes in cathode chamber fixed nitrogen
In ammonification reaction, H+Ion is provided by Bipolar Membrane intermediate layer water decomposition, the consumption of Bipolar Membrane intermediate layer water decomposition
Water is provided by anode chamber's electrolyte aqueous solution.Photoelectrocatalysis fixed nitrogen is carried out in non-aqueous solution, effectively inhibits liberation of hydrogen side reaction
Generation.
Compared with prior art, the invention has the following advantages:
1, the device and method of a kind of photoelectrocatalysis fixed nitrogen synthesis ammonia provided by the invention, carries out photoelectricity in non-aqueous solution
It is catalyzed fixed nitrogen, effectively inhibits the generation of liberation of hydrogen side reaction；
2, the device and method of a kind of photoelectrocatalysis fixed nitrogen synthesis ammonia provided by the invention, utilizes Bipolar Membrane water decomposition technology
H is provided for the reaction of photoelectrocatalysis fixed nitrogen+Ion, and by regulation Bipolar Membrane water decomposition rate, it both can guarantee that fixed nitrogen synthesis ammonia was anti-
Needed for answering, and it can be avoided H+The excessively high generation evolving hydrogen reaction of ion concentration, reaches H+The purpose of ion " produce and disappear ".
3, the device and method of a kind of photoelectrocatalysis fixed nitrogen synthesis ammonia provided by the invention, has using cation-exchange membrane liquid
Nanometer fixed nitrogen catalyst is secured in cation-exchange membrane surface by sticking feature, effectively avoids nanocatalyst that group occurs
Poly- phenomenon.
4, a kind of device and method of photoelectrocatalysis fixed nitrogen synthesis ammonia provided by the invention, the photoelectric compound film of preparation have
Light transmission is conducive to fully absorbing for photon, further increases photoelectrocatalysis efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of photoelectrocatalysis fixed nitrogen synthetic ammonia installation of the present invention；
Fig. 2 is the section SEM figure of Bipolar Membrane；
Fig. 3 is the photoelectric compound film photo figure under xenon lamp irradiation；
Fig. 4 is the sodium carboxymethylcellulose crosslinking schematic diagram that embodiment 1 prepares cation-exchange membrane；
Fig. 5 is the chitosan and glutaraldehyde cross-linking schematic diagram that embodiment 1 prepares anion-exchange membrane；
Fig. 6 is porous g-C of the embodiment 1 by pyrolysis urea method preparation3N4Nanometer fixed nitrogen catalyst SEM figure.
Specific embodiment
With reference to the accompanying drawing and pass through specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art
Member understands the present invention it will be clearly understood that the specific embodiment is only to aid in, and should not be regarded as a specific limitation of the invention.
Embodiment 1:
As shown in Figures 1 to 3, a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation comprising be catalyzed by Bipolar Membrane and nanometer fixed nitrogen
Anode chamber and cathode chamber are divided into two-compartment cell by the photoelectric compound film of film composition, the Bipolar Membrane include anion-exchange membrane and
Cation-exchange membrane, nanometer fixed nitrogen catalyst film are carried on cation-exchange membrane surface, and electrolyte aqueous solution is added in anode chamber,
Cathode chamber is full of nitrogen, with BiVO4Electrode fills dilute sulphur as cathode, cathode chamber setting as anode, fixed nitrogen catalyst film
The container of acid, for absorbing the ammonia of generation, using 300W xenon lamp as light source, external dc power supply provides electric field action power,
Anode, the cathode of DC power supply are connect with anode and cathode respectively.
Wherein, the photoelectric compound film the preparation method is as follows:
(1) anion-exchange membrane is prepared: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion
Support rib of the mixture of one or more of exchanger resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane
Frame, primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as anion-exchange membrane
Fixed group prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, method particularly includes:
It will gather as the polyvinyl alcohol of anion-exchange membrane support frame with the shell as anion-exchange membrane fixed group
Ratio of the sugar with mass ratio for 1:1, which is mixed, to be dissipated in container, and the aqueous acetic acid that mass fraction is 0.05% is added, stirs lower heat
It is dissolved to 60 DEG C, stands deaeration in 2 hours until completely dissolved, be then cast and done on clean band frame glass plate in smooth, used
The glutaraldehyde water solution that mass fraction is 5% is crosslinked, and volume is the 1/6 of anion exchange film liquid, dry in 60 DEG C of air blast
It is dried in dry case, obtaining area is 5 × 5cm2, with a thickness of 30 μm of anion-exchange membrane.Chitosan and glutaraldehyde cross-linking are illustrated
Figure is as shown in Figure 5.
(2) it prepares cation-exchange membrane: being appointed using one or more of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene
Support frame of the mixture of meaning ratio as cation-exchange membrane, one or more of sulfonic group, carboxylic acid group and phosphate
Fixed group of the mixture of arbitrary proportion as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step (1)
The anion exchange film surface of middle preparation, obtains cation-exchange membrane, method particularly includes:
It will be as the polyvinyl alcohol of cation-exchange membrane support frame and as the carboxylic first of cation-exchange membrane fixed group
Ratio of the base sodium cellulosate with mass ratio for 1:1, which is mixed, to be dissipated in container, and the phosphate aqueous solution that mass fraction is 0.05% is added, stirs
It mixes down and is heated to 60 DEG C of dissolutions, stand deaeration in 2 hours until completely dissolved and form cation-exchange membrane liquid, be then cast in step
(1) in prepare anion exchange film surface, use mass fraction for 5% FeCl3Aqueous solution is crosslinked, volume be sun from
The 1/6 of proton exchange liquid, it is 5 × 5cm that area is obtained after dry2, with a thickness of 30 μm of cation-exchange membrane.Carboxymethyl cellulose
It is as shown in Figure 4 that sodium is crosslinked schematic diagram.
(3) it prepares nanometer fixed nitrogen catalyst film: being loaded nanometer fixed nitrogen catalyst fines using spin-coating method or spray coating method
In cation-exchange membrane surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm.Method particularly includes:
Porous g-C is prepared by being pyrolyzed urea method3N4Nanometer fixed nitrogen catalyst, as shown in fig. 6, by the list after ultrasound removing
Layer g-C3N4Nanocatalyst is scattered in Nafion solution, and the cation-exchange membrane surface prepared in step (2) is selected to be in half
Dry state, when surface also has viscosity, by g-C3N4Nafion solution is sprayed at cation-exchange membrane surface, obtain with a thickness of
0.1 μm of g-C3N4Nano-catalytic agent film.
Light transmittance instrument is used to measure the light transmittance of photoelectric compound film as 76.4%.
A kind of fixed nitrogen synthesis ammonia method using photoelectrocatalysis fixed nitrogen synthetic ammonia installation, is specifically added concentration for anode chamber
For 0.10mol L-1Na2SO4Aqueous solution is full of nitrogen as electrolyte, cathode chamber, and sun is inserted into using BiVO4 electrode as anode
It is connected in pole room electrolyte with DC power anode and oxidation reaction, g-C occurs3N4Nanometer fixed nitrogen catalyst film as cathode simultaneously
It is connect with the cathode of DC power supply and nitrogen reduction reaction occurs, in cathode chamber fixed nitrogen ammonia synthesis reaction, H+ ion passes through Bipolar Membrane
Intermediate layer water decomposition provides, and the water of Bipolar Membrane intermediate layer water decomposition consumption is provided by anode chamber's electrolyte aqueous solution,
The container for filling dilute sulfuric acid is arranged in cathode chamber, for absorbing the ammonia of generation, is irradiated using the xenon lamp of 300W as light source, additional
The voltage of DC power supply is 0.5V, and under applied voltage effect, cathode chamber carries out photoelectrocatalysis fixed nitrogen and synthesizes ammonia, the ammonia of generation
0.1mol L is filled with cathode chamber-1The container of dilute sulfuric acid is absorbed, and uses nessler reagent development process combination LC-MS pair
Fixed nitrogen rate is analyzed.
Embodiment 2:
As shown in Figures 1 to 3, a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation comprising be catalyzed by Bipolar Membrane and nanometer fixed nitrogen
Anode chamber and cathode chamber are divided into two-compartment cell by the photoelectric compound film of film composition, the Bipolar Membrane include anion-exchange membrane and
Cation-exchange membrane, nanometer fixed nitrogen catalyst film are carried on cation-exchange membrane surface, and electrolyte aqueous solution is added in anode chamber,
Cathode chamber is full of nitrogen, with BiVO4Electrode fills dilute sulphur as cathode, cathode chamber setting as anode, fixed nitrogen catalyst film
The container of acid, for absorbing the ammonia of generation, using 300W xenon lamp as light source, external dc power supply provides electric field action power,
Anode, the cathode of DC power supply are connect with anode and cathode respectively.
Wherein, the photoelectric compound film the preparation method is as follows:
(1) anion-exchange membrane is prepared: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion
Support rib of the mixture of one or more of exchanger resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane
Frame, primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as anion-exchange membrane
Fixed group prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, method particularly includes:
It will be as the polypyrrole alkanone of anion-exchange membrane support frame and the season as anion-exchange membrane fixed group
Ammonium polysulfones is mixed with the ratio of mass ratio 2:1 to be dissipated in container, and the aqueous acetic acid that mass fraction is 0.1% is added, and stirring is lower to be added
Heat to 60 DEG C dissolve, until completely dissolved stand deaeration in 2 hours formed anion exchange film liquid, be then cast in it is smooth do it is clean
On band frame glass plate, mass fraction is used to be crosslinked for 6% glutaraldehyde water solution, volume is anion exchange film liquid
1/6, it is dried in 60 DEG C of air dry oven, obtaining area is 4 × 4cm2, with a thickness of 50 μm of anion-exchange membrane.
(2) it prepares cation-exchange membrane: being appointed using one or more of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene
Support frame of the mixture of meaning ratio as cation-exchange membrane, one or more of sulfonic group, carboxylic acid group and phosphate
Fixed group of the mixture of arbitrary proportion as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step (1)
The anion exchange film surface of middle preparation, obtains cation-exchange membrane, method particularly includes:
It will be fine as the polyphenylene oxide of cation-exchange membrane support frame and the acetic acid as cation-exchange membrane fixed group
Ratio of the dimension element with mass ratio for 2:1, which is mixed, to be dissipated in container, and the phosphate aqueous solution that mass fraction is 0.1% is added, and stirring is lower to be added
Heat is dissolved to 60 DEG C, is stood deaeration in 2 hours until completely dissolved and is formed cation-exchange membrane liquid, is then cast in step (1)
The anion exchange film surface of preparation, use mass fraction for 7% FeCl3Aqueous solution is crosslinked, and volume is that cation is handed over
The 1/6 of film liquid is changed, it is 4 × 4cm that area is obtained after dry2, with a thickness of 40 μm of cation-exchange membrane.
(3) it prepares nanometer fixed nitrogen catalyst film: being loaded nanometer fixed nitrogen catalyst fines using spin-coating method or spray coating method
In cation-exchange membrane surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm.Method particularly includes:
It disperses Ru/BiOCl nano-composite catalyst in Nafion solution, selects the cation prepared in step (2)
Exchange film surface is in leather hard, and when surface also has viscosity, Ru/BiOCl-Nafion solution spraying is exchanged in cation
Film surface obtains the Ru/BiOCl nano-catalytic agent film with a thickness of 0.6 μm.
Light transmittance instrument is used to measure the light transmittance of photoelectric compound film as 56.3%.
A kind of fixed nitrogen synthesis ammonia method using photoelectrocatalysis fixed nitrogen synthetic ammonia installation, is specifically added concentration for anode chamber
For 0.5mol L-1NaOH aqueous solution as electrolyte, cathode chamber is full of nitrogen, the insertion anode using BiVO4 electrode as anode
Be connected in the electrolyte of room with DC power anode and oxidation reaction occur, Ru/BiOCl nanometers of fixed nitrogen catalyst films as cathode simultaneously
It is connect with the cathode of DC power supply and nitrogen reduction reaction occurs, in cathode chamber fixed nitrogen ammonia synthesis reaction, H+ ion passes through Bipolar Membrane
Intermediate layer water decomposition provides, and the water of Bipolar Membrane intermediate layer water decomposition consumption is provided by anode chamber's electrolyte aqueous solution,
The container for filling dilute sulfuric acid is arranged in cathode chamber, for absorbing the ammonia of generation, is irradiated using the xenon lamp of 300W as light source, additional
The voltage of DC power supply is 0.8V, and under applied voltage effect, cathode chamber carries out photoelectrocatalysis fixed nitrogen and synthesizes ammonia, the ammonia of generation
0.5mol L is filled with cathode chamber-1The container of dilute sulfuric acid is absorbed, and uses nessler reagent development process combination LC-MS pair
Fixed nitrogen rate is analyzed.
Embodiment 3:
As shown in Figures 1 to 3, a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation comprising be catalyzed by Bipolar Membrane and nanometer fixed nitrogen
Anode chamber and cathode chamber are divided into two-compartment cell by the photoelectric compound film of film composition, the Bipolar Membrane include anion-exchange membrane and
Cation-exchange membrane, nanometer fixed nitrogen catalyst film are carried on cation-exchange membrane surface, and electrolyte aqueous solution is added in anode chamber,
Cathode chamber is full of nitrogen, and using Pt electrode as anode, fixed nitrogen catalyst film fills dilute sulfuric acid as cathode, cathode chamber setting
Container, for absorbing the ammonia of generation, using 300W xenon lamp as light source, external dc power supply provides electric field action power, direct current
Anode, the cathode of power supply are connect with anode and cathode respectively.
Wherein, the photoelectric compound film the preparation method is as follows:
(1) anion-exchange membrane is prepared: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion
Support rib of the mixture of one or more of exchanger resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane
Frame, primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as anion-exchange membrane
Fixed group prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, method particularly includes:
It will be as the styrene of anion-exchange membrane support frame and the chitosan as anion-exchange membrane fixed group
Ratio with mass ratio for 1:2, which is mixed, to be dissipated in container, and the aqueous acetic acid that mass fraction is 0.2% is added, is heated under stirring
60 DEG C of dissolutions stand deaeration in 2 hours until completely dissolved and form anion exchange film liquid, are then cast and do clean band edge in smooth
On frame glass plate, mass fraction is used to be crosslinked for 8% glutaraldehyde water solution, volume is the 1/6 of anion exchange film liquid,
It is dried in 60 DEG C of air dry oven, obtaining area is 6 × 6cm2, with a thickness of 60 μm of anion-exchange membrane.
(2) it prepares cation-exchange membrane: being appointed using one or more of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene
Support frame of the mixture of meaning ratio as cation-exchange membrane, one or more of sulfonic group, carboxylic acid group and phosphate
Fixed group of the mixture of arbitrary proportion as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step (1)
The anion exchange film surface of middle preparation, obtains cation-exchange membrane, method particularly includes:
It will be fine as the styrene of cation-exchange membrane support frame and the phosphoric acid as cation-exchange membrane fixed group
Ratio of the dimension element with mass ratio for 1:2, which is mixed, to be dissipated in container, and the phosphate aqueous solution that mass fraction is 0.08% is added, and stirring is lower to be added
Heat is dissolved to 60 DEG C, is stood deaeration in 2 hours until completely dissolved and is formed cation-exchange membrane liquid, is then cast in step (1)
The anion exchange film surface of preparation uses mass fraction to be crosslinked for 9% FeCl3 aqueous solution, and volume is that cation is handed over
The 1/6 of film liquid is changed, it is 6 × 6cm that area is obtained after dry2, with a thickness of 55 μm of cation-exchange membrane.
(3) it prepares nanometer fixed nitrogen catalyst film: being loaded nanometer fixed nitrogen catalyst fines using spin-coating method or spray coating method
In cation-exchange membrane surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm.Method particularly includes:
It disperses Ru nano-composite catalyst in Nafion solution, selects the cation-exchange membrane prepared in step (2)
Surface is in leather hard, and when surface also has viscosity, Ru-Nafion solution is spun on cation-exchange membrane surface, obtains
With a thickness of 0.2 μm of Ru nano-catalytic agent film.
Light transmittance instrument is used to measure the light transmittance of photoelectric compound film as 36.8%.
A kind of fixed nitrogen synthesis ammonia method using photoelectrocatalysis fixed nitrogen synthetic ammonia installation, is specifically added concentration for anode chamber
For 0.30mol L-1KOH aqueous solution as electrolyte, cathode chamber is full of nitrogen, and it is electric that anode chamber is inserted into using Pt electrode as anode
It is connected in solution liquid with DC power anode and oxidation reaction occurs, Ru nanometers of fixed nitrogen catalyst films is as cathode and and DC power supply
Cathode connection occur nitrogen reduction reaction, in cathode chamber fixed nitrogen ammonia synthesis reaction, H+ ion pass through Bipolar Membrane intermediate layer
Water decomposition provides, and the water of Bipolar Membrane intermediate layer water decomposition consumption is provided by anode chamber's electrolyte aqueous solution, cathode chamber setting
The container of dilute sulfuric acid is filled, for absorbing the ammonia of generation, is irradiated using the xenon lamp of 300W as light source, external dc power supply
Voltage is 1.0V, and under applied voltage effect, cathode chamber carries out photoelectrocatalysis fixed nitrogen and synthesizes ammonia, and the ammonia of generation is contained with cathode chamber
There is 1.0mol L-1The container of dilute sulfuric acid is absorbed, and using nessler reagent development process combination LC-MS to fixed nitrogen rate into
Row analysis.
Embodiment 4:
As shown in Figures 1 to 3, a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation comprising be catalyzed by Bipolar Membrane and nanometer fixed nitrogen
Anode chamber and cathode chamber are divided into two-compartment cell by the photoelectric compound film of film composition, the Bipolar Membrane include anion-exchange membrane and
Cation-exchange membrane, nanometer fixed nitrogen catalyst film are carried on cation-exchange membrane surface, and electrolyte aqueous solution is added in anode chamber,
Cathode chamber is full of nitrogen, and using Pt electrode as anode, fixed nitrogen catalyst film fills 1.0mol as cathode, cathode chamber setting
L-1The container of dilute sulfuric acid, for absorbing the ammonia of generation, using 300W xenon lamp as light source, external dc power supply provides electric field and makees
Firmly, the anode of DC power supply, cathode are connect with anode and cathode respectively.
Wherein, the photoelectric compound film the preparation method is as follows:
(1) anion-exchange membrane is prepared: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion
Support rib of the mixture of one or more of exchanger resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane
Frame, primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as anion-exchange membrane
Fixed group prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, method particularly includes:
By as the polysulfones of anion-exchange membrane support frame with as anion-exchange membrane fixed group chitosan with
The ratio that mass ratio is 1:3 is mixed to be dissipated in container, and the aqueous acetic acid that mass fraction is 0.2% is added, is heated to 60 under stirring
DEG C dissolution, stands deaeration in 2 hours until completely dissolved and forms anion exchange film liquid, be then cast and do clean band frame in smooth
On glass plate, mass fraction is used to be crosslinked for 10% glutaraldehyde water solution, volume is the 1/6 of anion exchange film liquid,
It is dried in 60 DEG C of air dry oven, obtaining area is 6 × 6cm2, with a thickness of 80 μm of anion-exchange membrane.
(2) it prepares cation-exchange membrane: being appointed using one or more of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene
Support frame of the mixture of meaning ratio as cation-exchange membrane, one or more of sulfonic group, carboxylic acid group and phosphate
Fixed group of the mixture of arbitrary proportion as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step (1)
The anion exchange film surface of middle preparation, obtains cation-exchange membrane, method particularly includes:
It will be fine as the polysulfones of cation-exchange membrane support frame and the carboxymethyl as cation-exchange membrane fixed group
It ties up ratio of the plain sodium with mass ratio for 1:2 and mixes and dissipate in container, the phosphate aqueous solution that mass fraction is 0.06% is added, under stirring
60 DEG C of dissolutions are heated to, deaeration in 2 hours is stood until completely dissolved and forms cation-exchange membrane liquid, be then cast in step (1)
The anion exchange film surface of middle preparation, use mass fraction for 10% FeCl3Aqueous solution is crosslinked, and volume is cation
The 1/6 of film liquid is exchanged, it is 6 × 6cm that area is obtained after dry2, with a thickness of 80 μm of cation-exchange membrane.
(3) it prepares nanometer fixed nitrogen catalyst film: being loaded nanometer fixed nitrogen catalyst fines using spin-coating method or spray coating method
In cation-exchange membrane surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm.Method particularly includes:
It disperses Mg-Al nano-composite catalyst in Nafion solution, selects the cation exchange prepared in step (2)
Film surface is in leather hard, and when surface also has viscosity, Mg-Al-Nafion solution is spun on cation-exchange membrane surface,
Obtain the Mg-Al nano-catalytic agent film with a thickness of 2 μm.
Light transmittance instrument is used to measure the light transmittance of photoelectric compound film as 30%.
A kind of fixed nitrogen synthesis ammonia method using photoelectrocatalysis fixed nitrogen synthetic ammonia installation, is specifically added concentration for anode chamber
For 2.0mol L-1KOH aqueous solution as electrolyte, cathode chamber is full of nitrogen, and it is electric that anode chamber is inserted into using Pt electrode as anode
It is connected in solution liquid with DC power anode and oxidation reaction occurs, Mg-Al nanometers of fixed nitrogen catalyst films is as cathode and and direct current
Nitrogen reduction reaction occurs for the cathode connection of power supply, and in cathode chamber fixed nitrogen ammonia synthesis reaction, H+ ion passes through boundary in Bipolar Membrane
Surface layer water decomposition provides, and the water of Bipolar Membrane intermediate layer water decomposition consumption is provided by anode chamber's electrolyte aqueous solution, cathode chamber
The container for filling dilute sulfuric acid is set, for absorbing the ammonia of generation, is irradiated using the xenon lamp of 300W as light source, applying direct current
The voltage in source is 2.0V, and under applied voltage effect, cathode chamber carries out photoelectrocatalysis fixed nitrogen and synthesizes ammonia, the ammonia cathode of generation
Room fills 1.0mol L-1The container of dilute sulfuric acid is absorbed, and using nessler reagent development process combination LC-MS to fixed nitrogen speed
Rate is analyzed.
In a particular embodiment, when preparing anion-exchange membrane, support frame substance is not limited only to polyvinyl alcohol, polypyrrole
Alkanone, styrene and polysulfones, can also select one of polyphenylene oxide, polysulfones, anion exchange resin, polyethylene benzyl chloride or
Support frame of the mixture of several arbitrary proportions as anion-exchange membrane；Fixed group is not limited only to chitosan and quaternary ammonium is poly-
Sulfone, can also select primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as yin from
The fixed group of proton exchange；And support frame substance and fixed group substance can arbitrary proportion mixed preparing anion exchanges
Film liquid.When preparing cation-exchange membrane, support frame substance is not limited only to polyvinyl alcohol, polyphenylene oxide, styrene and polysulfones, may be used also
Using the mixture for several arbitrary proportions selected in polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene as cation-exchange membrane
Support frame；Fixed group is not limited only to the sodium carboxymethylcellulose, cellulose phosphate and cellulose acetate of carboxylic acid group, can be with
Select fixation of the mixture of one or more of sulfonic group, carboxylic acid group and phosphate arbitrary proportion as cation-exchange membrane
Group；And support frame substance and fixed group substance can arbitrary proportion mixed preparing cation-exchange membrane liquid.Nanometer fixed nitrogen
Catalyst film is not limited to g-C3N4, Ru and Mg-Al, can also select BiOCl, BiOBr, Fe, Co, Ni, Ni-Fe, Zn-Cr or
One of Zn-Al layered double hydroxide or its is several compound.
Claims (10)
1. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation, it is characterised in that: the light being made of Bipolar Membrane and nanometer fixed nitrogen catalytic membrane
Anode chamber and cathode chamber are divided into two-compartment cell by electric composite membrane, and the Bipolar Membrane includes anion-exchange membrane and cation exchange
Film, nanometer fixed nitrogen catalyst film are carried on cation-exchange membrane surface, and electrolyte aqueous solution is added in anode chamber, and cathode chamber is full of
Nitrogen, with BiVO4Or Pt electrode, as anode, the appearance for filling dilute sulfuric acid is arranged as cathode, cathode chamber in fixed nitrogen catalyst film
Device, for absorbing the ammonia of generation, using xenon lamp as light source, external dc power supply provides electric field action power, DC power supply
Anode, cathode are connect with anode and cathode respectively.
2. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 1, it is characterised in that: the photoelectric compound film
The preparation method is as follows:
(1) anion-exchange membrane is prepared: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene, anion exchange
Support frame of the mixture of one or more of resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane, primary
Amino, secondary amino group, tertiary amino and quaternary ammonium one or more of arbitrary proportions fixation of the mixture as anion-exchange membrane
Group prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, with a thickness of 30~80 μm；
(2) cation-exchange membrane is prepared: using any ratio of one or more of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene
Support frame of the mixture of example as cation-exchange membrane, one or more of sulfonic group, carboxylic acid group and phosphate are any
Fixed group of the mixture of ratio as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step (1) preparation
Anion exchange film surface, cation-exchange membrane is obtained, with a thickness of 30~80 μm；
(3) it prepares nanometer fixed nitrogen catalyst film: nanometer fixed nitrogen catalyst fines is carried on by sun using spin-coating method or spray coating method
Ion exchange film surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm.
3. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 2, it is characterised in that: the photoelectric compound film
Preparation method in, (1) prepares anion-exchange membrane: using polyvinyl alcohol, polypyrrole alkanone, polyphenylene oxide, polysulfones, styrene,
Branch of the mixture of one or more of anion exchange resin, polyethylene benzyl chloride arbitrary proportion as anion-exchange membrane
Support bone frame, primary amino group, secondary amino group, tertiary amino, quaternary ammonium one or more of arbitrary proportions mixture as anion exchange
The fixed group of film prepares anion exchange film liquid and prepares anion-exchange membrane by the tape casting, with a thickness of 30~80 μm；Tool
Body method are as follows:
It dissipates being mixed as the substance of anion-exchange membrane support frame with the substance as anion-exchange membrane fixed group in appearance
In device, the aqueous acetic acid that mass fraction is 0.05%~0.2% is added, 60 DEG C of dissolutions are heated under stirring, wait be completely dissolved
Deaeration in 2 hours is stood afterwards and forms anion exchange film liquid, is then cast and is done on clean band frame glass plate in smooth, using quality
The glutaraldehyde water solution that score is 5~10% is crosslinked, and volume is the 1/6 of anion exchange film liquid, dry in 60 DEG C of air blast
It is dried in dry case, obtains anion-exchange membrane.
4. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 3, it is characterised in that: the photoelectric compound film
Preparation method in, (2) prepare cation-exchange membrane: using one of polyvinyl alcohol, polyphenylene oxide, polysulfones and styrene or several
Support frame of the mixture of kind of arbitrary proportion as cation-exchange membrane, one of sulfonic group, carboxylic acid group and phosphate or
Fixed group of the mixture of several arbitrary proportions as cation-exchange membrane is prepared cation-exchange membrane liquid and is cast in step
(1) the anion exchange film surface prepared in, obtains cation-exchange membrane, with a thickness of 30~80 μm；Method particularly includes:
It dissipates being mixed as the substance of cation-exchange membrane support frame with the substance as cation-exchange membrane fixed group in appearance
In device, the phosphate aqueous solution that mass fraction is 0.05%~0.1% is added, 60 DEG C of dissolutions are heated under stirring, wait be completely dissolved
Deaeration in 2 hours is stood afterwards and forms cation-exchange membrane liquid, is then cast the anion exchange film surface prepared in step (1),
Use mass fraction for 5~10% FeCl3Aqueous solution is crosslinked, and volume is the 1/6 of cation-exchange membrane liquid, is obtained after dry
To cation-exchange membrane.
5. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 4, it is characterised in that: the photoelectric compound film
Preparation method in, (3) prepare nanometer fixed nitrogen catalyst film: using spin-coating method or spray coating method by nanometer fixed nitrogen catalyst fines
It is carried on cation-exchange membrane surface, nanometer fixed nitrogen catalyst film is with a thickness of 0.1~2.0 μm；Method particularly includes:
It disperses nano-catalyst particles in Nafion solution, selects at cation-exchange membrane surface prepared by step (2)
In leather hard, when surface also has viscosity, it will spray or be spun on containing the Nafion solution of nanometer fixed nitrogen catalyst granules
Cation-exchange membrane surface obtains a nanometer fixed nitrogen catalyst film.
6. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 5, it is characterised in that: the nanometer fixed nitrogen
Catalyst film includes BiOCl, BiOBr, g-C3N4, the double gold of Fe, Co, Ni, Ru, Mg-Al, Ni-Fe, Zn-Cr or Zn-Al stratiform
Belong to the mixture of one of hydroxide or two or more arbitrary proportions.
7. a kind of photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 1 to 6, it is characterised in that: described
Photoelectric compound film have light transmission, light transmittance be 30%~76.4%.
8. a kind of fixed nitrogen using photoelectrocatalysis fixed nitrogen synthetic ammonia installation synthesizes ammonia method, it is characterised in that: anode chamber to be added
Electrolyte aqueous solution, cathode chamber are full of nitrogen, connect using BiVO4 or Pt electrode as anode and with the anode of DC power supply, Gu
Nitrogen catalyst film is connect as cathode and with the cathode of DC power supply, and it is 0.1~1.0mol L that cathode chamber setting, which fills concentration,-1
The container of dilute sulfuric acid is irradiated using xenon lamp as light source, the voltage of external dc power supply is 0.5 for absorbing the ammonia of generation
~2.0V.
9. a kind of fixed nitrogen using photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 8 synthesizes ammonia method, special
Sign is: the electrolyte aqueous solution is Na2SO4, NaOH or KOH aqueous solution, the electrolyte aqueous solution concentration are
0.10~2.0mol L-1。
10. a kind of fixed nitrogen using photoelectrocatalysis fixed nitrogen synthetic ammonia installation according to claim 9 synthesizes ammonia method, special
Sign is: the BiVO4Or be connected in Pt electrode insertion anode chamber's electrolyte with positive pole and oxidation reaction occurs, nanometer is solid
Nitrogen catalyst film, which is connected as cathode with power cathode, occurs nitrogen reduction reaction, in cathode chamber fixed nitrogen ammonia synthesis reaction, H+
Ion is provided by Bipolar Membrane intermediate layer water decomposition, and the water of Bipolar Membrane intermediate layer water decomposition consumption is electrolysed by anode chamber
Matter aqueous solution provides.
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