CN105749914B - A kind of method of symmetrical difunctional photochemical catalyst, dual chamber Photoreactor and photocatalytic reduction of carbon oxide - Google Patents
A kind of method of symmetrical difunctional photochemical catalyst, dual chamber Photoreactor and photocatalytic reduction of carbon oxide Download PDFInfo
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- CN105749914B CN105749914B CN201610159514.0A CN201610159514A CN105749914B CN 105749914 B CN105749914 B CN 105749914B CN 201610159514 A CN201610159514 A CN 201610159514A CN 105749914 B CN105749914 B CN 105749914B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 230000009977 dual effect Effects 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 36
- 230000009467 reduction Effects 0.000 title claims description 9
- 229910002090 carbon oxide Inorganic materials 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000006722 reduction reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002047 photoemission electron microscopy Methods 0.000 claims description 5
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000007539 photo-oxidation reaction Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 3
- 239000012159 carrier gas Substances 0.000 claims 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- 238000007704 wet chemistry method Methods 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 24
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- -1 graphite alkene Chemical class 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 9
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940116367 cadmium sulfide Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229960001296 zinc oxide Drugs 0.000 description 1
- 229910006654 β-PbO2 Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of symmetrical difunctional photochemical catalyst and corresponding dual chamber Photoreactor, belong to Utilization of Carbon Dioxide technical field, wherein symmetrical difunctional photochemical catalyst includes two-sided TiO2Deposited graphite alkene central electron transport layer in nano-tube array substrate, redeposited low-gap semiconductor nano particle is as photosensitizer.Symmetrical photochemical catalyst provided by the invention makes the photoresponse of Three-element composite photocatalyst expand to visible region by the introducing of electron transfer layer and photosensitizer component, photo-generate electron-hole is promoted to efficiently separating simultaneously, enhances composite catalyst photo catalytic reduction CO2Ability；The double-sided symmetrical ternary complex catalyst makes photocatalysis water oxygen and CO after dual chamber Photoreactor is matched2Reduction reaction is carried out in independent region respectively, reduces the generation of back reaction, further improves photocatalysis CO2Reduction efficiency.
Description
Technical field
It is more particularly to a kind of symmetrical difunctional photochemical catalyst, double the invention belongs to Utilization of Carbon Dioxide technical field
The method of room Photoreactor and photocatalytic reduction of carbon oxide.
Background technology
Energy shortage and carbon dioxide（CO2）The greenhouse effects of initiation, which have become, threatens social development and people daily
The subject matter of life, but simultaneously, because the CO of rich reserves2Itself it is also a kind of important industrial chemicals, it is how efficiently wide
It is general by its trans-utilization to there has been proposed challenge and opportunity.However, due to CO2Chemical property itself is stable, it is necessary to extra
The energy input could be activated and be converted into useful compound.Solar energy be it is a kind of clean, it is cheap, widely distributed can
The renewable sources of energy, using solar energy photocatalytic technology by CO2Solar energy fuel is reduced to, for alleviating energy shortage, improving ecology
Environment is all of great significance.
Photo catalytic reduction CO at present2Research focus primarily upon two aspect：The structure of photochemical catalyst and setting for reactor
Meter.In the photochemical catalyst applied at present, research more generally powder-type catalyst.Although powder-type catalyst preparation side
Method is simple, good product dispersibility, but recovery is difficult, product inconvenience separates, photogenerated charge is easily compound, photocatalysis efficiency is low etc. be present
Shortcoming.Therefore, the immobilization for powder photocatalyst and the research of film base catalyst just turn into focus.Because photoelectrocatalysis is made
With can largely lift CO2Reduction efficiency, thus be widely studied.But the maximum deficiency of photo-electrocatalytic technology exactly needs
Additional electric energy is wanted to input, which adds overall energy consuming and equipment cost.Meanwhile under External Electrical Field, membrane electrode
It itself may also can trigger side reaction, have considerable influence for the stability of catalyst.In view of problem above, seeks a kind of efficient
Stable film based photocatalyst is to influence photo catalytic reduction CO2Technology can industrial applications key.
Another influences photo-reduction CO2The factor of technology is exactly the design of reactor.Efficient film based photocatalyst needs
There is the cooperation of the Photoreactor for its Optimal Structure Designing, the photocatalytic system so formed could play it to greatest extent also
Former CO2Ability.Relative to traditional single chamber photo catalysis reactor, two-compartment reactor can effectively make redox products only
It is vertical to produce, reduce the generation of back reaction and side reaction, improve photocatalysis CO2Reduction efficiency.At present, two-compartment reactor more should
For photoelectrocatalytioxidation oxidation system, CO is realized only with photocatalytic process2The patent report of reduction is also less.Chinese patent
CN103348039A discloses one kind photo catalytic reduction CO in two-compartment reactor2Method, using nitride semiconductor layers as
Anode, indium or indium compound are negative electrode, are connected two single photochemistry electrodes by external wire.But in the invention due to outer
The presence of wire is connect, makes whole device complicated, and light conversion efficiency is reduced due to wire voltage drop and fuel factor.
Chinese patent CN103898548A discloses one kind and utilizes graphene and TiO2The method of nanotube photoelectrocatalysis reduction, to mix Pt
It is graphene-supported in being used as electric negative electrode, TiO in nickel foam2Nano-tube array is attached to Nafion respectively as light anode, and by it
Catalyst electrode is made in the both sides of PEM, is positioned between two-compartment reactor, while applied voltage enters in cathode and anode
Row photoelectrocatalysis reduces CO2Application.The energy entirely reacted is both similarly made due to the presence of additional circuit in the invention
The increase of input, the loss of energy may can be produced in electron transfer process again.
The content of the invention
It is an object of the invention to provide a kind of symmetrical difunctional photochemical catalyst and corresponding dual chamber Photoreactor, there is provided light
The method of catalysis reduction carbon dioxide is then another object of the present invention.
Based on above-mentioned purpose, the present invention adopts the following technical scheme that：A kind of symmetrical difunctional photochemical catalyst, including by pure titanium
Two-sided TiO is prepared by two step anodizings2Nano-tube array（TNA）Film substrate, substrate surface electro-deposition have graphite
Alkene layer, graphene layer are electron transfer layer, change graphene deposit thickness by regulating and controlling electrochemical parameter, regulation and control electronics exists
Transmission in the difunctional photochemical catalyst of composite symmetrical, improve photoelectron-hole to recombination probability again；Then sunk on graphene layer
Product low-gap semiconductor nano particle is as photosensitizer.
Preferably, the low-gap semiconductor nano particle is cuprous oxide, cupric oxide, cadmium sulfide, zinc oxide, vulcanization
The mixing of one or both of lead, lead oxide and the above.
Preferably, the method for the electro-deposition is cyclic voltammetry, galvanostatic deposition method or potentiostatic electrodeposition method.
Preferably, the method that low-gap semiconductor nano particle is deposited on graphene layer is electrochemical deposition, wet-chemical
Method deposition, hydro-thermal method deposition, solvent-thermal method deposition or photochemical method deposition.
Using the dual chamber Photoreactor of above-mentioned symmetrical difunctional photochemical catalyst, including symmetrically arranged anode reaction pond and the moon
Pole reaction tank, two connectors are provided between cathode reaction pond and anode reaction pond, are fixed among a connector
Nafion PEMs, the substrate made of symmetrical difunctional photochemical catalyst, negative electrode are fixed among another connector
Air inlet and gas outlet are equipped with the top of reaction tank and anode reaction pond, anode reaction pond side wall is provided with light window.
Further, it is water or electrolyte solution in anode reaction pond and cathode reaction pond, the electrolyte in anode reaction pond
Solution is Na2SO4、NaCl、Na2SO3The mixture of one or both of solution and the above；The electrolyte in cathode reaction pond is molten
Liquid is NaHCO3、Na2CO3、NaOH、KOH、K2CO3The mixture of one or both of solution and the above.
Further, the side wall in cathode reaction pond is provided with liquid taking port, is examined by liquid taking port or gas outlet with gas-chromatography
Survey analysis liquid phase or vapour phase reduction products collection efficiency.
Using the method for above-mentioned dual chamber Photoreactor photocatalytic reduction of carbon oxide, comprise the following steps：It is anti-in dual chamber light
The anode reaction pond and cathode reaction pond for answering device add water or electrolyte solution；By catalyst substrates and Nafion PEMs
It is clamped in respectively on two connectors of reactor, makes that anode reaction pond and cathode reaction pond are directly not connected, and only proton can
Flowed by Nafion membrane between two ponds；Direct irradiation is on substrate after light injects anode reaction pond by light window, high-purity N2、
CO2Gas is each passed through by air inlet in the electrolyte solution in anode reaction pond, cathode reaction pond respectively, and gas-phase product is with load
Gas discharges reactor by gas outlet, forms a continuous feed, the photo catalytic reduction CO of opening2Reaction system；Light source（Including purple
Outer light, visible ray or full spectrum light source）The photosensitizer on substrate is excited to produce photoelectron-hole pair, electronics on anode surface
Migrated respectively to photochemical catalyst to cathode plane transmission, hole and electronics by the effect of the energy level alignment and electron transfer layer of matching
Anode surface and cathode plane, in the reaction tank of independent separate participate in water photooxidation and CO2Reduction reaction.
Further, CO2Reduzate be alcohols, the mixing of hydro carbons, one or both of carbon monoxide and the above
Thing.
The present invention uses TiO2Nano-tube array（TNA）For substrate, convenient directly application, recovery and replacing, pass through introducing
Electron transfer layer and photosensitizer component, the photoresponse of Three-element composite photocatalyst is expanded to visible region, promote simultaneously
Photo-generate electron-hole enhances composite catalyst photo catalytic reduction CO to efficiently separating2Ability；Urged in matching dual chamber light
Redox reaction is carried out respectively in independent region after changing reactor, reduce the generation of back reaction, further improve light
It is catalyzed CO2Reduction efficiency.In addition, the present invention is not required to additional electric energy input, energy consumption is reduced.
Meanwhile barrier film of the present invention using the difunctional photochemical catalyst of double-sided symmetrical directly as dual chamber Photoreactor, save
Go external circuit to connect, by the formation of multiple heterojunction boundary in catalyst, efficiently separate photogenerated charge, improve CO2Reduction
Efficiency, photo-reduction CO is carried out using this system2Document yet there are no report.
Brief description of the drawings
Fig. 1 is the preparation flow figure of symmetrical difunctional photochemical catalyst；
Fig. 2 is the scanning electron microscope (SEM) photograph that sample is prepared in embodiment 1, wherein（a）For TNA electron-microscope scanning exterior view；（b）For
G/TNA electron-microscope scanning exterior view；（c）For Cu2O/G/TNA electron-microscope scanning exterior view；（d）For Cu2O/G/TNA Electronic Speculum is swept
Retouch sectional drawing；
Fig. 3 is dual chamber photo catalysis reactor front view；
Fig. 4 is the top view of dual chamber photo catalysis reactor；
Fig. 5 is the left view of dual chamber photo catalysis reactor；
Fig. 6 is that symmetrical difunctional photochemical catalyst carries out photo catalytic reduction CO in dual chamber Photoreactor2Schematic diagram；
Fig. 7 is obtained Cu in embodiment 1,6,7,82O/G/TNA、CdS/G/TNA、PbO2/ G/TNA, ZnO/G/TNA exists
Photo catalytic reduction CO in reactor shown in Fig. 3 ~ 52Methanol output.
Embodiment
With reference to embodiment the present invention is described further explain.
Embodiment 1
1. symmetrical difunctional Cu2The preparation of O/G/TNA film photocatalysts
A kind of symmetrical difunctional photochemical catalyst, including two-sided TiO is prepared by two step anodizings by pure titanium2Receive
Mitron array（TNA）Film substrate, substrate surface electro-deposition have graphene layer, are sunk by regulating and controlling electrochemical parameter to change graphene
Lamination thickness, so as to regulate and control transmission of the electronics in the difunctional photochemical catalyst of composite symmetrical, improve photoelectron-hole to compound again
Probability；Then low-gap semiconductor nano particle is deposited on graphene layer as photosensitizer, its preparation process such as Fig. 1 institutes
Show, comprise the following steps：
（1）Prepare TNA film substrates：By pure titanium foil after physics is polished and is cleaned by ultrasonic, soaked in chemical pickling liquid
Carry out chemical polishing；Then it is 0.25% NH titanium foil to be placed in into mass fraction4In F ethylene glycol-water mixed solution, wherein second two
Alcohol is 49 with water volume ratio：1, it is clear through deionized water after carrying out anodic oxidation twice under similarity condition using three-electrode system
Wash and dry, be placed in Muffle furnace, air atmosphere 500o2 h are calcined under C, finally give double-sided symmetrical TNA film substrates.Its Electronic Speculum
Shown in scanning of a surface figure such as Fig. 2 (a), it can be seen that TNA film substrates top layer regular appearance, aperture is homogeneous, and bottom is nanotube
Array, aperture are about 30 nm, and pipe range is in 500 nm or so；
（2）Prepare G/TNA substrates（Deposited graphite alkene）：In the three-electrode system using TNA film substrates as working electrode,
Graphene sheet layer is deposited on by TNA films surface, scanning voltage scope in graphene oxide aqueous dispersions using cyclic voltammetry
For -1.5~+1 V, the scanning number of turns is 20 circles, and producing deposition has the TNA film substrates (G/TNA) of graphene.Its electron-microscope scanning surface
Figure is as shown in Fig. 2 (b), obvious graphene feature pleated structure and TNA surfaces shape under its coverage as we can see from the figure
Looks, thus prove that certain thickness thin graphene is deposited to TNA surfaces；
（3）Prepare Cu2O/G/TNA substrates（In G/TNA substrate deposition low-gap semiconductor nano particles）：Using electrochemistry
Sedimentation is by Cu2O nanoparticle depositions are in G/TNA surfaces, deposition Cu2O electrolyte is CuSO4Lactic acid aqueous solution, CuSO4
Concentration be 0.4 mol/L, the concentration of lactic acid is 3 mol/L, pH value is adjusted into 10 by 5 mol/L NaOH, deposition voltage
For -0.4 V, sedimentation time is 600 s.After the completion of deposition, with deionized water rinsing, drying, that is, double-sided symmetrical Cu is obtained2O/G/
TNA film photocatalysts, it is designated as sample 1.Its electron-microscope scanning exterior view such as Fig. 2（c）It is shown, Cu as we know from the figure2O nano particles are equal
Even to be distributed in graphene layer surface, particle diameter is about 80 nm；Its electron-microscope scanning one side sectional drawing such as Fig. 2（d）It is shown, as seen from the figure,
Graphene layer and Cu2O nano particles are successfully deposited at TNA surface and form Three-element composite photocatalyst Cu successively2O/G/
TNA。
Dual chamber Photoreactor
Dual chamber Photoreactor, its structure is as shown in Fig. 3 ~ 5, including anode reaction pond A and cathode reaction pond B.Face south respectively
1 mol/L Na is added in pole reaction tank A and cathode reaction pond B2SO4And NaHCO3Solution is as electrolyte, anode reaction pond A
Clamping Nafion PEMs, make anode reaction pond and cathode reaction pond straight among connector 7 between the B of cathode reaction pond
Connect not connected, only proton can be flowed by Nafion membrane between two ponds；Clamping Cu among connector 62O/G/TNA film light is urged
Substrate made of agent；The first air inlet 1 and the first gas outlet 2, anode reaction pond A side walls are equipped with the top of the A of anode reaction pond
It is provided with light window 8；The second air inlet 3 and the second gas outlet 4 are equipped with the top of the B of cathode reaction pond, side wall is provided with liquid taking port
5。
Photo catalytic reduction CO2Experiment
The 300 W xenon lamps to add 400 nm ultraviolet cut-on filter plates are used as light source（λ>400 nm）, it is high after reaction starts
Pure N2Enter anode reaction pond A from the first air inlet 1, discharged from the first gas outlet 2, CO2It is anti-to enter negative electrode from the second air inlet 3
Pond B to be answered, is discharged from the second gas outlet 4, the photosensitizer on light source activation substrate produces photoelectron-hole pair on anode surface,
The effect of energy level alignment and electron transfer layer that electronics passes through matching migrates to light urge respectively to cathode plane transmission, hole and electronics
The anode surface and cathode plane of agent, photooxidation and the CO of water are participated in the reaction tank of independent separate2Reduction reaction, photocatalysis
Reduce CO2Process schematic is as shown in Figure 6.Every 1 h, 10 μ L reaction solutions are taken out from liquid taking port 5, samples 6 times, passes through outfit
The gas-chromatography for having flame ionic detector carries out product analysis detection, refers to using liquid product methanol output as catalytic performance test
Mark, it is respectively 67.5,125,148,180,223 and 275 μm of ol/cm that its yield, which is calculated,2, concrete outcome is shown in Fig. 7.
Embodiment 2 ~ 5
The method that embodiment 2,3,4,5 prepares TNA film substrates is same as Example 1, prepares G/TNA substrates and Cu2O/G/
The process reference implementation example 1 of TNA substrates, specific technological parameter are shown in Table 1, corresponding Cu2O/G/TNA substrates are labeled as sample successively
Product 2, sample 3, sample 4, sample 5.
Sample 2, sample 3, sample 4, sample are clamped among the connector 6 of the dual chamber Photoreactor of embodiment 2,3,4,5 respectively
The electrolyte solution species of injection is shown in Table 1 in product 5, anode reaction pond A and cathode reaction pond B.
The photo catalytic reduction CO of embodiment 2,3,4,52The process for preparing methanol experiment is same as Example 1.
The process parameter table of the embodiment 1 ~ 5 of table 1
Embodiment 6
The preparation process of G/TNA film substrates is identical with the preparation process of embodiment 1.
CdS is deposited on G/TNA surfaces using hydrothermal deposition method, process is：Compound concentration is 0.004mol/L chlorine respectively
The aqueous solution of the cadmium aqueous solution and thiocarbamide, the ratio for being 1: 3 in the aqueous solution (the amount ratio of material) of caddy Shui Rong Ye ︰ thiocarbamides
Uniformly mixing.The vertical fixed placement of G/TNA film substrates adds caddy and thiocarbamide mixed solution in autoclave, will be close
The reactor being honored as a queen is placed in 170 DEG C of baking ovens, and the reaction time is 6 h.After completion of the reaction take out sample cleaned with distilled water after
400 DEG C of 3 h of heat treatment, are made CdS/G/TNA film substrates in Ar atmosphere.
Clamping CdS/G/TNA film substrates, photo catalytic reduction CO among the connector 6 of dual chamber Photoreactor2Prepare methanol,
Specific product detection analysis process is same as Example 1, and it is respectively 52,78,110,130,151,170 that methanol output, which is calculated,
μmol/cm2, concrete outcome is shown in Fig. 7.
Embodiment 7
The preparation process of G/TNA film substrates is identical with the preparation process of embodiment 1.
ZnO is deposited on G/TNA surfaces using photochemical precipitation method, process is：Configuration concentration is 0.5 mol/L zinc nitrate water
Solution, G/TNA film substrates are immersed in zinc nitrate solution vertically, 15 min are irradiated simultaneously to substrate two sides under uviol lamp, taken
It is placed at 100 DEG C and is dried in vacuo after being cleaned up after going out with deionized water, then 450 DEG C of 1 h of heat treatment in an ar atmosphere, produce
The ZnO/G/TNA film substrates prepared using photochemical precipitation method.
Clamping ZnO/G/TNA film substrates, photo catalytic reduction CO among the connector 6 of dual chamber Photoreactor2Prepare methanol,
Specific product detection analysis process is same as Example 1, and it is respectively 12.5,20,26,29,30,31 μ that methanol output, which is calculated,
mol/cm2, concrete outcome is shown in Fig. 7.
Embodiment 8
The preparation process of G/TNA film substrates is identical with the preparation process of embodiment 1.
PbO is prepared using electrochemical deposition method2/ G/TNA film substrates, process are：First prepare electroplate liquid：Nitric acid in electroplate liquid
The concentration of lead is 20.5 mol/L, and the concentration of nitric acid is 0.1 mol/L, and the concentration of sodium fluoride is 0.04 mol/L, then by G/
TNA substrates are placed in electroplate liquid, using three-electrode system, implement pulse electrodeposition, and temperature is 333 K, mixing speed 300
R/min, the min of electro-deposition 10, produces β-PbO2The G/TNA substrates of modification, i.e. PbO2/ G/TNA film substrates.
The clamping PbO among the connector 6 of dual chamber Photoreactor2/ G/TNA film substrates, photo catalytic reduction CO2Prepare methanol,
Specific product detection analysis process is same as Example 1, and it is respectively 40,51,55,68,73,75 μ that methanol output, which is calculated,
mol/cm2, concrete outcome is shown in Fig. 7.
Claims (8)
1. using the dual chamber Photoreactor of symmetrical difunctional photochemical catalyst, it is characterised in that the symmetrical difunctional photochemical catalyst
Including TiO2Nano-tube array substrate, substrate surface electro-deposition have graphene layer, and being deposited on graphene layer has low-gap semiconductor
Nano particle is as photosensitizer；It is anti-including symmetrically arranged anode reaction pond and cathode reaction pond, cathode reaction pond and anode
Two connectors are provided between Ying Chi, Nafion PEMs are fixed among a connector, in another connector
Between be fixed with the substrate made of symmetrical difunctional photochemical catalyst, be equipped with air inlet at the top of cathode reaction pond and anode reaction pond
Mouth and gas outlet, anode reaction pond side wall are provided with light window.
2. dual chamber Photoreactor according to claim 1, it is characterised in that the low-gap semiconductor nano particle is oxygen
Change the mixing of one or both of cuprous, cupric oxide, cadmium sulfide, zinc oxide, vulcanized lead, lead oxide and the above.
3. dual chamber Photoreactor according to claim 1 or 2, it is characterised in that the method for the electro-deposition lies prostrate for circulation
An Fa, galvanostatic deposition method or potentiostatic electrodeposition method.
4. dual chamber Photoreactor according to claim 3, it is characterised in that low-gap semiconductor is deposited on graphene layer
The method of nano particle is that electrochemical deposition, wet chemistry method deposition, hydro-thermal method deposition, solvent-thermal method deposition or photochemical method sink
Product.
5. according to the dual chamber Photoreactor described in claim 1 or 2 or 4, it is characterised in that anode reaction pond and cathode reaction pond
In be water or electrolyte solution, the electrolyte solution in anode reaction pond is Na2SO4、NaCl、Na2SO3One kind in solution or two
The mixture of kind and the above；The electrolyte solution in cathode reaction pond is NaHCO3、Na2CO3、NaOH、KOH、K2CO3One in solution
Kind or two kinds and the above mixture.
6. dual chamber Photoreactor according to claim 5, it is characterised in that the side wall in cathode reaction pond is provided with and takes liquid
Mouthful.
7. using the method for the dual chamber Photoreactor photocatalytic reduction of carbon oxide described in claim 6, it is characterised in that：Double
The anode reaction pond of room Photoreactor and cathode reaction pond add water or electrolyte solution；Light injects anode reaction by light window
Direct irradiation is on substrate behind pond, high-purity N2、CO2Gas is each passed through anode reaction pond, cathode reaction pond by air inlet respectively
Electrolyte solution in, enter photooxidation and the CO of water-filling2Reduction reaction；Gas-phase product is discharged with carrier gas by gas outlet to react
Device.
8. the method for photocatalytic reduction of carbon oxide according to claim 7, it is characterised in that CO2Reduzate be alcohol
The mixture of one or both of class, hydro carbons, carbon monoxide and the above.
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| CN111041523B (en) * | 2020-01-02 | 2021-09-07 | 东莞理工学院 | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water |
| CN112354496A (en) * | 2020-11-27 | 2021-02-12 | 天津大学 | Building emission reduction reactor based on photoelectrocatalysis system |
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