CN109438156A - Method for dehalogenation conversion of halogenated hydrocarbon by photocatalysis - Google Patents
Method for dehalogenation conversion of halogenated hydrocarbon by photocatalysis Download PDFInfo
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- CN109438156A CN109438156A CN201811639457.1A CN201811639457A CN109438156A CN 109438156 A CN109438156 A CN 109438156A CN 201811639457 A CN201811639457 A CN 201811639457A CN 109438156 A CN109438156 A CN 109438156A
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- Prior art keywords
- halogenated hydrocarbons
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- dehalogenation
- photocatalysis
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 78
- 150000008282 halocarbons Chemical class 0.000 title claims abstract description 63
- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 23
- 239000002096 quantum dot Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 103
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 41
- -1 alkenyl halide Chemical class 0.000 claims description 33
- 229910004613 CdTe Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 4
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 claims description 3
- 229910018038 Cu2ZnSnSe4 Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003570 air Substances 0.000 claims 1
- 229910017053 inorganic salt Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 13
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 abstract description 7
- 229910052805 deuterium Inorganic materials 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 55
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 38
- 239000012298 atmosphere Substances 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- 238000006073 displacement reaction Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZJJATABWMGVVRZ-UHFFFAOYSA-N 1,12-dibromododecane Chemical compound BrCCCCCCCCCCCCBr ZJJATABWMGVVRZ-UHFFFAOYSA-N 0.000 description 1
- FRWYJOLIZIMTGP-UHFFFAOYSA-N 1,3-dibromo-1,1,2-trichloropropane Chemical compound ClC(C(Cl)(Cl)Br)CBr FRWYJOLIZIMTGP-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- BPBNKCIVWFCMJY-UHFFFAOYSA-N 1-ethynyl-4-phenylbenzene Chemical group C1=CC(C#C)=CC=C1C1=CC=CC=C1 BPBNKCIVWFCMJY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- 229910003256 NaTaO3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QTBSBXVTEAMEQO-GUEYOVJQSA-N acetic acid-d4 Chemical compound [2H]OC(=O)C([2H])([2H])[2H] QTBSBXVTEAMEQO-GUEYOVJQSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000036267 drug metabolism Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- 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
-
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds 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
- 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/001—Acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for dehalogenation and conversion of halogenated hydrocarbon by photocatalysis, which comprises the following steps: adding the photocatalyst quantum dots/rods into a solvent to obtain a solution A; adding halogenated hydrocarbon and an electronic sacrificial body into the solution A to obtain a solution B; and (3) irradiating the solution B with a light source to catalyze the dehalogenation conversion of the halogenated hydrocarbon. The invention uses the nanometer quantum dots and the nanometer quantum rods for the dehalogenation conversion reaction of halogenated alkane, halogenated alkene and halogenated alkyne for the first time, the reaction condition is mild, the visible light is used as the driving energy, the product is a hydrocarbon compound, and the whole process is green, simple and efficient; in addition, higher hydrocarbon with an increased carbon chain can be generated after dehalogenation reaction, and the potential application of the method in the preparation of higher hydrocarbon is reflected. The invention combines the processes of halogenated hydrocarbon dehalogenation conversion and deuterium marking for the first time, completes the deuterium marking of the hydrocarbon while completing the halogenated hydrocarbon dehalogenation process, and provides a method for carrying out deuterium marking on the hydrocarbon.
Description
Technical field
The invention belongs to catalyze and synthesize and the sustainable development technical field of environment and the energy, it is related to a kind of photocatalysis halogen
For the method for hydrocarbon dehalogenation conversion.
Background technique
Halogenated hydrocarbons, such as methylene chloride, trichloro ethylene, methylene bromide, are industrially widely used in pesticide, medicine, polymerization
The production of object and dyestuff and pigment.It is largely discharged into environment, the danger of duration can be caused to ecological environment and human-body safety
Evil.The effective means for handling halogenated hydrocarbons is hydro-reduction.It is said from thermodynamics, hydro-reduction halogenated hydrocarbons is endothermic process, is needed
More energy are provided.Currently used method is that noble metal is catalyst, realizes that the dehalogenation of halogenated hydrocarbons adds under hot conditions
Hydrogen conversion.Such as: professor Rodriguez be prepared for a kind of Pt/C catalyst (Rodriguez, J.J.etc J.Catal.2011,
279,389.), under 250 DEG C of high temperature and hydrogen, the dechlorination for realizing methylene chloride is converted into methane, is selectively up to
85%.This catalyst stability with higher continued the hydrogenation-dechlorination reaction for being efficiently catalyzed methylene chloride at 26 days.
Professor McFarland is prepared for a kind of Pd6C/SiO2Catalyst (Ding, K.；Derk,A.R.；Zhang,A.；Hu,Z.；
Stoimenov,P.；Stucky,G.D.；Metiu,H.；McFarland, E.W.ACS Catal.2012,2,479.), by hydrogen
With methylene bromide under 350 DEG C of hot conditions, 19% C is realized2The selectivity of hydrocarbon.Other than Pd, Pt, metal
Ru, Re, Ir etc. are fixed on aluminium oxide, titanium dioxide, silica or active carbon, and realize alkylene dihalide adds hydrogen
Dehalogenation.But above-mentioned reaction system has used noble metal, and the reaction condition that need high temperature and hydrogen etc. harsh, generation
The perishable consersion unit of pernicious gas HCl and lure catalyst easy in inactivation into.
For reduced reaction temperature, the halogenated alkane dehalogenation hydro-conversion under temperate condition is realized, scientists start
Realize that halogenated alkane dehalogenation converts using photocatalytic system.Such as, professor Doong is prepared for Fe/TiO2Nanocomposite
(Doong, R.-a.etc.Appl Catal B-environ 2010,100,116.) realizes three under deep ultraviolet light irradiation
The dechlorination of vinyl chloride is converted into ethane, but rate is only 0.013h-1.Pd-Au is then loaded to TiO by professor Balint2On
(State,R.；Papa,F.；Tabakova,T.；Atkinson,I.；Negrila,C.；Balint,I.J.Catal.2017,
346,101.), although realizing the efficient dechlorination (> 80%) of trichloro ethylene, its product is mainly CO2.Domen group is then
Look for another way, is prepared for multi-functional Pd-NiO/NaTaO3: La catalyst (O ' Keefe, W.K.；Liu,Y.；Sasges,
M.R.；Wong,M.S.；Fu,H.；Takata,T.；Domen, K.Ind.Eng.Chem.Res.2014,53,9600.), use original
The hydrogen that position generates, is successfully realized the dechlorination hydro-conversion of carbon tetrachloride, product is mainly methane.But the reaction system
Efficiency is lower, and concentration of substrate is only ppm rank.Accordingly, it is desirable to provide a kind of new halogenated hydrocarbons dehalogenation method.
Deuterated label is an important technology, is usually used in the important tool of drug metabolism analysis and exploratory response mechanism.
The main method for realizing the deuterated label of hydrocarbon compound is direct H/D exchange.For example, professor Yu is catalysis using precious metal palladium
Agent realizes benzyl position deuterated (Engle, the K.M. of phenylacetic acid class compound using deuterated acetic acid as deuterium source；Thuy-Boun,P.S.；
Dang,M.；Yu,J.-Q.,J.Am.Chem.Soc.2011,133,18183-18193.)；Macmillian group then uses gold
Category iridium is photosensitizer, and deuterated label (McNally, the A. at aminated compounds ortho position are realized using deuterium-oxide as deuterium source；Prier,
C.K.；MacMillan,D.W.C.,.Science 2011,334,1114-1117.).But these systems have many disadvantages,
It is such as narrow using noble metal, substrate use scope.Therefore it needs to provide a kind of new deuterated labeling method of hydro carbons.
Summary of the invention
First purpose of the invention is to provide a kind of method of photocatalysis halogenated hydrocarbons dehalogenation conversion.This method is in illumination item
Under part, under the catalytic action of nano material quantum dot or quantum rod, in the presence of electronics sacrificial body, directly carbon-halogen bond can be turned
Corresponding C-H bond or carbon-carbon bond are turned to, realizes dehalogenation conversion.This method can be realized at room temperature in daylight, and be used
Catalyst be quantum dot or quantum rod, do not include precious metal, have it is viable economically, without toxic waste generate and react
The advantages of mild condition.
Second object of the present invention is to provide a kind of method of photocatalysis halogenated hydrocarbons dehalogenation conversion and deuterated label, can
So that halogenated hydrocarbons completes deuterated label while completing dehalogenation conversion, the deuterated label of hydro carbons is realized.
In the present invention, the halogenated hydrocarbons includes halogenated alkane, alkenyl halide or halogenated alkynes.C in halogenated hydrocarbon molecule
Atom number, the position of branch, the number of branch, the type of branch, the type of halogeno-group, the position of halogeno-group, halogeno-group
Number, the position of carbon-carbon double bond and number, the position of triple carbon-carbon bonds and number can be converted in the dehalogenation in light-catalyzed reaction,
Carbon-halogen bond in halogenated hydrocarbon molecule can be converted into C-H bond or carbon-carbon bond.
In the present invention, under photocatalysis, carbon-halogen bond can be converted into C-H bond, can also be converted into carbon-carbon bond.
When carbon-halogen bond is converted into corresponding C-H bond, products therefrom is corresponding halogenated hydrocarbons；When carbon-halogen bond is converted into carbon-carbon bond, institute
Obtaining product is the higher hydrocarbon that corresponding carbochain increases.
It selects nano-quantum point or the Nano quantum stick as photochemical catalyst in the present invention, is used in the prior art
The noble metals such as ruthenium, iridium are compared, and have apparent viable economically property；And the reaction efficiency can achieve 90%；And product is hydrocarbon
Class compound, the halogen after reaction are completely converted into anion, have the advantages that environmentally protective.With TiO2System is compared, and is utilized
Visible light, product are the higher chemicals of economic value, avoid the generation of the by-products such as carbon dioxide, more meet Green Chemistry
Demand.
It is including following the present invention provides a kind of method of photocatalysis halogenated hydrocarbons dehalogenation conversion to reach first purpose
Step:
Photochemical catalyst is added in solvent, solution A is obtained；
Halogenated hydrocarbons and electronics sacrificial body are added in solution A, solution B is obtained；
Solution B is irradiated with light source, catalysis carries out the conversion of halogenated hydrocarbons dehalogenation；
Wherein, the halogenated hydrocarbons includes halogenated alkane, alkenyl halide or halogenated alkynes；The photochemical catalyst includes quantum
Point/stick.
Especially, it should be noted that electronics sacrificial body described in the present invention is to refer not only to photocatalytically, energy
The substance of electronics is enough provided, photohole can be captured during the reaction, but also wants that matter can be provided during the reaction
Son serves as proton donor.
Preferably, the halogenated element contained in the halogenated hydrocarbons is selected from one of F, Cl, Br or I or a variety of.
Preferably, the halogenated hydrocarbons dehalogenation conversion is carried out under nitrogen or argon atmosphere.
In the present invention, after obtained solution B, nitrogen or argon gas can be replaced as air atmosphere, then carries out light
It is reacted according to catalysis.The conversion of halogenated hydrocarbons dehalogenation is carried out under nitrogen or argon atmosphere to be conducive to that photochemical catalyst is avoided to inactivate.
Preferably, the quantum dot/stick be selected from following quantum rod/one of or it is a variety of: CdSe, CdS, CdTe,
CdSexS1-x、CdSe/CdS、CdSe/ZnSe、CdSe/ZnS、CdS/ZnSe、CdS/ZnS、CdTe/ZnSe、CdTe/ZnS、
CdASe、CdAS、CdATe、CdSe/TiO2、CdS/TiO2、CdTe/TiO2、CdSe/g-C3N4、CdSe/CDs、CdSe/GO、
CdSe/RGO、CdSe/GY、CdS/g-C3N4、CdS/CDs、CdS/GO、CdS/RGO、CdS/GY、CdTe/g-C3N4、CdTe/
CDs、CdTe/GO、CdTe/RGO、CdTe/GY、InP、InP/CdS、InP/CdSe、InP/CdTe、InP/ZnS、InP/ZnSe、
InP/GaP、CuInS2、CuInS2/ZnS、CuInS2/ZnSe、CuInSe2、CuInSe2/ZnS、CuInSe2/ZnSe、
Cu2ZnSnS4、Cu2ZnSnSe4、CsPbX3、CsSnX3、Cs2SnI6、Cs3Bi2X9、M3Sb2X9、Cs2AgBiY6、CH3NH3PbX3、HC
(NH2)PbY3；Wherein, value range 0.088≤x≤0.375 of the x, the A is selected from one of Fe, Co, Ni, described
CDs represents Carbon Quantum Dots, and GO represents Graphene Oxide, and RGO represents Reductive Graphene
Oxide, GY represent Graphdiyne, and the X is selected from one of Cl, Br, I, and the Y is selected from one of Br or I, the M
Selected from one of Cs or Rb.
It should be noted that when quantum dot provided by the invention/stick catalyst is made of more than one quantum dot/stick
Hybridized quantum dot/stick when, the present invention to form hybridized quantum dot/stick each component ratio with no restriction, as long as can
Dehalogenation conversion is realized as catalyst, just within protection scope of the present invention.If hybridized quantum dot/stick CdSe/CdS is by measuring
Sub- point/stick CdS is supported on to be obtained on quantum dot/stick CdSe, and " CdSe/CdS " expression is supported on by " CdSe " on " CdS "
The composite quantum dot arrived/stick CdSe/CdS, and it is not specific to the ratio of " CdSe " and " CdS " in composite quantum dot/stick CdSe/CdS
It is 1:1, there is no limit meanings for ratio of " CdSe/CdS " this general formula to " CdSe " and " CdS ".
Preferably, the solvent includes the mixed solvent of organic solvent, water or organic solvent and water.The present invention is to organic molten
With no restriction, i.e. organic solvent and water can be mixed the mixed proportion of agent and water with arbitrary proportion.
Preferably, the electronics sacrificial body includes aminated compounds, alcohol compound or inorganic salts；
Preferably, the aminated compounds includes three-level aminated compounds, secondary-amine compound, primary amine compound or virtue
Fragrant amine class compound；
Preferably, the alcohol compound includes methanol, ethyl alcohol or isopropanol；
Preferably, the inorganic salts include sulphite, sulfide or nitrite.
Preferably, the photochemical catalyst in the concentration in solution B zero between saturated concentration, and do not include zero；It is described
Halogenated hydrocarbons arrives between saturation molar concentration in the molar concentration in solution B zero, and does not include zero；
It is highly preferred that molar concentration of the photochemical catalyst in solution B is 5 × 10-4M~1 × 10-7M；Preferably, institute
Stating molar concentration of the halogenated hydrocarbons in solution B is 0.001M~10M.
During dehalogenation, after carbon-halogen bond fracture, also along with halogen yin in the generating process of C-H bond or carbon-carbon bond
The generation of ion, the generation of halide anion need electronics sacrificial body to provide electronics for it, in the present invention, to electric in solution B
In sub- sacrificial body and halogenated hydrocarbons the ratio of the amount of the substance of halogen atom with no restrictions, for example, when the electronics sacrificial body with it is described
When the mass ratio of the material of halogen atom is greater than 1:1 in halogenated hydrocarbons, electronics sacrificial body can provide enough at this time for halide anion
Electronics.
Preferably, the light source includes sunlight, LED light, medium pressure mercury lamp, high-pressure sodium lamp or xenon lamp.
The second aspect of the present invention provides the method for a kind of conversion of photocatalysis halogenated hydrocarbons dehalogenation and deuterated label, including with
Lower step:
Photochemical catalyst is added in solvent, solution A is obtained；
Halogenated hydrocarbons and electronics sacrificial body are added in solution A, solution B is obtained；
Solution B is irradiated with light source, catalysis carries out the conversion of halogenated hydrocarbons dehalogenation；
Wherein, the halogenated hydrocarbons includes halogenated alkane, alkenyl halide or halogenated alkynes；The photochemical catalyst includes quantum
Point/stick；Wherein, the dehalogenation conversion process solvent for use includes the mixed solvent of heavy water or organic solvent and heavy water or deuterated has
The mixed solvent of solvent or deuterated organic solvent and heavy water.
Preferably, the electronics sacrificial body is selected from the one or more of following compounds: deuterated aminated compounds, deuterated
Alcohol compound and inorganic salts.Preferably, the deuterated aminated compounds include three-level aminated compounds, secondary-amine compound,
Primary amine compound or aromatic amine compounds；Preferably, the deuterated alcohol compound includes methanol, ethyl alcohol or isopropanol；
Preferably, the inorganic salts include sulphite, sulfide or nitrite.
Preferably, the halogenated element contained in the halogenated hydrocarbons is selected from one of F, Cl, Br or I or a variety of.
Preferably, the halogenated hydrocarbons dehalogenation conversion is carried out under nitrogen or argon atmosphere.
In the present invention, after obtained solution B, nitrogen or argon gas can be replaced as air atmosphere, then carries out light
It is reacted according to catalysis.The conversion of halogenated hydrocarbons dehalogenation is carried out under nitrogen or argon atmosphere to be conducive to that photochemical catalyst is avoided to inactivate.
Preferably, the quantum dot/stick be selected from following quantum rod/one of or it is a variety of: CdSe, CdS, CdTe,
CdSexS1-x、CdSe/CdS、CdSe/ZnSe、CdSe/ZnS、CdS/ZnSe、CdS/ZnS、CdTe/ZnSe、CdTe/ZnS、
CdASe、CdAS、CdATe、CdSe/TiO2、CdS/TiO2、CdTe/TiO2、CdSe/g-C3N4、CdSe/CDs、CdSe/GO、
CdSe/RGO、CdSe/GY、CdS/g-C3N4、CdS/CDs、CdS/GO、CdS/RGO、CdS/GY、CdTe/g-C3N4、CdTe/
CDs、CdTe/GO、CdTe/RGO、CdTe/GY、InP、InP/CdS、InP/CdSe、InP/CdTe、InP/ZnS、InP/ZnSe、
InP/GaP、CuInS2、CuInS2/ZnS、CuInS2/ZnSe、CuInSe2、CuInSe2/ZnS、CuInSe2/ZnSe、
Cu2ZnSnS4、Cu2ZnSnSe4、CsPbX3、CsSnX3、Cs2SnI6、Cs3Bi2X9、M3Sb2X9、Cs2AgBiY6、CH3NH3PbX3、HC
(NH2)PbY3；Wherein, value range 0.088≤x≤0.375 of the x, the A is selected from one of Fe, Co, Ni, described
CDs represents Carbon Quantum Dots, and GO represents Graphene Oxide, and RGO represents Reductive Graphene
Oxide, GY represent Graphdiyne, and the X is selected from one of Cl, Br, I, and the Y is selected from one of Br or I, the M
Selected from one of Cs or Rb.
Preferably, the photochemical catalyst in the concentration in solution B zero between saturated concentration, and do not include zero；It is described
Halogenated hydrocarbons arrives between saturation molar concentration in the molar concentration in solution B zero, and does not include zero；
More electedly, molar concentration of the photochemical catalyst in solution B is 5 × 10-4M~1 × 10-7M；Preferably, institute
Stating molar concentration of the halogenated hydrocarbons in solution B is 0.001M~10M.
Preferably, the light source includes LED light, medium pressure mercury lamp, high-pressure sodium lamp or xenon lamp.
The present invention provides one kind using quantum dot as photochemical catalyst, amine, alcohols or inorganic salts compound be hydrogen source and
Electronics sacrificial body, it is seen that the lower dehalogenation conversion for realizing efficient halogenated hydrocarbons of light irradiation.The system is by photocatalysis proton reduction and dehalogenation
Process uniformly combines, and realizes the dehalogenation conversion under halogenated hydrocarbons temperate condition, generates corresponding hydrocarbonylation object or higher hydrocarbon compound
Contour economic value chemicals.Halogen atom is converted into halide anion there are in reaction solution simultaneously, avoids corrosive gas
The generation of hydrogen halides has biggish application value.
In addition, the method for photocatalysis halogenated hydrocarbons dehalogenation conversion provided by the invention and deuterated label, this method is with inorganic salts
Class compound is electronics sacrificial body, real under visible light illumination using quantum dot or quantum rod as photochemical catalyst using heavy water as deuterium source
Now conversion of the carbon-halogen bond of efficient halogenated hydrocarbons to carbon deuterium key provides a kind of approach of completely new deuterated label hydro carbons.The hydrocarbon
The deuterated labeling method of class, reactivity site is unrestricted, can be realized simultaneously the deuterated label of multiple sites and atom, application
Range is wide.
Beneficial effects of the present invention are as follows:
1, quantum dot and quantum rod are used for the dehalogenation conversion reaction of halogenated alkane, alkenyl halide and halogenated alkynes for the first time.
2, the present invention for the first time converts halogenated hydrocarbons dehalogenation and deuterated labeling process merges progress, completes halogenated hydrocarbons dehalogenation mistake
The deuterated label that hydro carbons is completed while journey provides a kind of method that hydro carbons carries out deuterated label.
3, above two method provided by the invention all mild conditions, with visible light be driving can, realize halogenated alkane,
The conversion of the dehalogenation of alkenyl halide and halogenated alkynes, whole process is green, succinct, efficiently.
4, in dehalogenation method for transformation provided by the invention, the halogen after reaction is completely converted into anion, and halogenated hydrocarbons is then
It is converted into the higher hydrocarbon of corresponding hydrocarbon or carbochain growth, is being conducive to while recycling of halogen atom, is also complying with original
The sustainable development requirement of subeconomy principle and Green Chemistry.
5, the product of dehalogenation method for transformation provided by the invention first is that carbochain increase higher hydrocarbon, embody this method and exist
Potential application in the preparation of higher hydrocarbon.
Detailed description of the invention
Fig. 1 is absorption and the luminescent spectrum of CdSe quantum dot
Fig. 2 is that 2 photocatalysis methylene bromide of example adds the product of hydrogen debrominate to be distributed GC-FID figure；
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done below with reference to preferred embodiments and drawings further details of
Explanation.It will be appreciated by those skilled in the art that specifically described content is illustrative and be not restrictive below, it should not be with
This is limited the scope of the invention.
In the present invention photochemical catalyst reference literature report method prepare (H.Y.Han, Z.H.Sheng, J.L.Liang,
Materials Letters 2006,60,3782)。
Embodiment 1.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M,
The methylene chloride (66.3mg, 0.78mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L is added, air is set
Change Ar atmosphere, 1mL N into2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, it is examined with GC (TCD)
Survey CH4Yield.The yield of methane is 80%.
Embodiment 2.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the methylene bromide (135.6mg, 0.78mmol) of 55 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, air is set
Change Ar atmosphere, 1mL N into2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, it is detected with FID-GC
CH4With the selectivity and yield of ethylene.The selectivity of methane is 22%, and the selectivity of ethylene and ethane is up to 77%.
Embodiment 3.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the diiodomethane (208.9mg, 0.78mmol) of 63 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, air is set
Change Ar atmosphere, 1mL N into2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, it is detected with FID-GC
CH4With the selectivity and yield of ethylene.The selectivity of ethylene and ethane is up to 95%.
Embodiment 4.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter 1, the 2- Bromofume (109mg, 0.58mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, by air
It is replaced as Ar atmosphere, 1mL methane is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, FID-GC is used
Detection ethylene is primary product, and yield is up to 99%.
Embodiment 5.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter 1,12- dibromo-dodecane (164mg, 0.5mmol) and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, by air displacement
At Ar atmosphere, at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, diphenatril is internal standard, is detected with FID-GC
Dodecane is primary product, and yield is up to 90%.
Embodiment 6.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter 1, the 2- dibromotetrafluoroethane (108.8mg, 0.42mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L,
By air displacement at Ar atmosphere, 1mL methane is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, it uses
FID-GC detection has ethylene synthesis, and ion chromatography detects the generation of fluorine ion and bromide ion；
Embodiment 7.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the chloroform (74mg, 0.62mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, by air displacement at Ar gas
Atmosphere, 1mL nitrogen is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, it is with FID-GC detection methane
Primary product；
Embodiment 8.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the carbon tetrachloride (79.7mg, 0.52mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, by air displacement
At Ar atmosphere, 1mL nitrogen is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, it is detected with FID-GC
Methane primary product；
Embodiment 9.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the 2- N-Propyl Bromide (66.5mg, 0.54mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, by air displacement
At Ar atmosphere, 1mL methane is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, it is detected with FID-GC
Propane is primary product, and yield is up to 90%；
Embodiment 10.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter 1,2, the 3- trichloro ethylenes (73.2mg, 0.56mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 100 μ L, it will be empty
Gas is replaced as Ar atmosphere, and 1mL methane is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 2h.After reaction, FID- is used
It is primary product that GC, which detects ethylene,.
Embodiment 11.
Using CdSe/CdS core-shell quanta dots as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is
2×10-5M, be added 55 μ L methylene bromide (135.6mg, 0.78mmol) and 300 μ L triethylamine (218.1mg,
2.16mmol), by air displacement at Ar atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.Reaction
After, CH is detected with FID-GC4With the selectivity and yield of ethylene.It is 74% that the selectivity of methane, which is up to, ethylene and ethane
Selectivity be 26%.
Embodiment 12.
Using CdSe/ZnS quantum rod as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst be 2 ×
10-5The methylene bromide (135.6mg, 0.78mmol) of 55 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L is added in M, will
Air displacement is at Ar atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, FID- is used
The generation of GC detection methane, ethane and ethylene.
Embodiment 13.
With CdSe/TiO2For photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10- 5The methylene chloride (66.3mg, 0.78mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L is added in M, will be empty
Gas is replaced as Ar atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 12h.After reaction, GC is used
(FID) CH is detected4It generates.
Embodiment 14.
Using CuInZnS as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M,
The methylene chloride (66.3mg, 0.78mmol) of 50 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L is added, air is set
Change Ar atmosphere, 1mL N into2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 12h.After reaction, it is examined with GC (FID)
Survey CH4、C2H4、C2H6The generation of equal hydrocarbons.
Embodiment 15.
With perovskite CsPbBr3Quantum dot is photochemical catalyst, is added in 4mL chloroform, wherein the solubility of catalyst be 2 ×
10-5The triethylamine (218.1mg, 2.16mmol) of 300 μ L is added, by air displacement at Ar atmosphere, 1mL N in M2As internal standard, room
Under temperature, LED light (λ > 460nm) irradiates 12h.After reaction, C is detected with GC (FID)2H4、C3H8The production of equal hydrocarbons
It is raw.
Embodiment 16.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-4M adds
Enter the methylene bromide (135.6mg, 0.78mmol) of 55 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, air is set
Change Ar atmosphere, 1mL N into2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, it is detected with FID-GC
CH4With the selectivity and yield of ethylene.The selectivity of methane is 32%, and the selectivity of ethylene and ethane is up to 64%.
Embodiment 17.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-7M adds
Enter the methylene bromide (135.6mg, 0.78mmol) of 55 μ L and the triethylamine (218.1mg, 2.16mmol) of 300 μ L, air is set
Change Ar atmosphere, 1mL N into2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, it is detected with FID-GC
CH4With the selectivity and yield of ethylene.The selectivity of methane is 42%, and the selectivity of ethylene and ethane is up to 48%.
Embodiment 18.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M,
The methylene chloride (66.3mg, 0.78mmol) and sodium sulfite (295mg, 2.34mmol) of 50 μ L is added, by air displacement at Ar
Atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, CH is detected with GC (TCD)4It produces
It is raw.
Embodiment 19.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the methylene bromide (135.6mg, 0.78mmol) of 55 μ L and the diisopropylethylamine amine (156.4mg, 1.21mmol) of 200 μ L,
By air displacement at Ar atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, it uses
FID-GC detects CH4With the selectivity and yield of ethylene.The selectivity of methane is 74%, and the selectivity of ethylene and ethane is up to
25%.
Embodiment 20.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter the methylene bromide (135.6mg, 0.78mmol) of 55 μ L and the isopropanol (157mg, 2.61mmol) of 200 μ L, by air displacement
At Ar atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, CH is detected with FID-GC4
With the selectivity and yield of ethylene.The selectivity of methane is 90%, and the selectivity of ethylene and ethane is 6.2%.
Embodiment 21.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
The methylene bromide (135.6mg, 0.78mmol) and ascorbic acid (200mg, 1.14mmol) for entering 55 μ L, by air displacement at Ar gas
Atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 8h.After reaction, CH is detected with FID-GC4And ethylene
Selectivity and yield.The selectivity of methane is 98%, and the selectivity of ethylene and ethane is 1.2%.
Embodiment 22.
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M adds
Enter 4- bromoacetylene base -1 of 50 μ L, the triethylamine of 1 '-biphenyl (51.2mg, 0.2mmol) and 100 μ L (218.1mg,
2.16mmol), by air displacement at Ar atmosphere, 1mL methane is as internal standard, and at room temperature, LED light (λ > 460nm) irradiates 8h.Reaction
After, with silica gel post separation, 4- acetenyl biphenyl is primary product, yield 84%.
Embodiment 23.
Using CdSe QDs as photochemical catalyst, it is added to the D of 4mLDMF and 2.4ML2In O, wherein the solubility of catalyst is
1.25×10-5The methylene chloride (66.3mg, 0.78mmol) and sodium sulfite (126.04mg, 1mmol) of 50 μ L is added in M, will be empty
Gas is replaced as Ar atmosphere, and at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, CD is detected with GC-MS2H2It generates.
Embodiment 24.
Using CdSe QDs as photochemical catalyst, it is added to the D of 4mLDMF and 2.4ML2In O, wherein the solubility of catalyst is
1.25×10-5The chloroform (74mg, 0.62mmol) and sodium sulfite (126.04mg, 1mmol) of 50 μ L is added, by air in M
It is replaced as Ar atmosphere, at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, CD is detected with GC-MS3H is generated.
Embodiment 25.
Using CdSe QDs as photochemical catalyst, it is added to the D of 4mLDMF and 2.4ML2In O, wherein the solubility of catalyst is
1.25×10-5The bromododecane (52mg, 0.21mmol) and sodium sulfite (126.04mg, 1mmol) of 50 μ L is added in M, will be empty
Gas is replaced as Ar atmosphere, and at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, D is detected with HNMR1Dodecane
It generates.
Embodiment 26.
Using CdSe QDs as photochemical catalyst, it is added to the D of 4mLDMF and 2.4ML2In O, wherein the solubility of catalyst is
1.25×10-5The Bian bromine (72mg, 0.42mmol) and sodium sulfite (126.04mg, 1mmol) of 50 μ L is added, by air displacement in M
At Ar atmosphere, at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, D is detected with GC-MS1The generation of toluene.
Embodiment 27
Using CdSe QDs as photochemical catalyst, photochemical catalyst is added in 4mL water, wherein the solubility of catalyst is 2 × 10-5M,
The methylene chloride (66.3mg, 0.78mmol) of 50 μ L and the deuterated triethylamine (218.1mg, 2.16mmol) of 300 μ L is added, it will be empty
Gas is replaced as Ar atmosphere, 1mL N2As internal standard, at room temperature, LED light (λ > 460nm) irradiates 4h.After reaction, GC-MS is used
Detect deuterated methane CH2D2It generates.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of method of photocatalysis halogenated hydrocarbons dehalogenation conversion, which comprises the following steps:
Photochemical catalyst is added in solvent, solution A is obtained；
Halogenated hydrocarbons and electronics sacrificial body are added in solution A, solution B is obtained；
Solution B is irradiated with light source, catalysis carries out the conversion of halogenated hydrocarbons dehalogenation；
Wherein, the halogenated hydrocarbons includes halogenated alkane, alkenyl halide or halogenated alkynes；The photochemical catalyst includes quantum dot/stick.
2. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that contain in the halogenated hydrocarbons
Halogen be one of F, Cl, Br or I or a variety of.
3. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that the halogenated hydrocarbons dehalogenation turns
Change is carried out under air or nitrogen or argon atmosphere.
4. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that the quantum dot/stick choosing
From following quantum rod/one of or it is a variety of: CdSe, CdS, CdTe, CdSexS1-x、CdSe/CdS、CdSe/ZnSe、CdSe/
ZnS、CdS/ZnSe、CdS/ZnS、CdTe/ZnSe、CdTe/ZnS、CdASe、CdAS、CdATe、CdSe/TiO2、CdS/TiO2、
CdTe/TiO2、CdSe/g-C3N4、CdSe/CDs、CdSe/GO、CdSe/RGO、CdSe/GY、CdS/g-C3N4、CdS/CDs、CdS/
GO、CdS/RGO、CdS/GY、CdTe/g-C3N4、CdTe/CDs、CdTe/GO、CdTe/RGO、CdTe/GY、InP、InP/CdS、
InP/CdSe、InP/CdTe、InP/ZnS、InP/ZnSe、InP/GaP、CuInS2、CuInS2/ZnS、CuInS2/ZnSe、
CuInSe2、CuInSe2/ZnS、CuInSe2/ZnSe、Cu2ZnSnS4、Cu2ZnSnSe4、CsPbX3、CsSnX3、Cs2SnI6、
Cs3Bi2X9、M3Sb2X9、Cs2AgBiY6、CH3NH3PbX3、HC(NH2)PbY3；Wherein, 0.088≤x of value range of the x≤
0.375, the A are selected from one of Fe, Co, Ni, and the CDs represents Carbon Quantum Dots, GO and represents Graphene
Oxide, RGO represent Reductive Graphene Oxide, and GY represents Graphdiyne, the X in Cl, Br, I one
Kind, the Y is selected from one of Br or I, and the M is selected from one of Cs or Rb.
5. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that the solvent includes organic
The mixed solvent of solvent, water or organic solvent and water.
6. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that the electronics sacrificial body choosing
From the one or more of following compounds: aminated compounds, alcohol compound or inorganic salts.Preferably, the aminated compounds
Including three-level aminated compounds, secondary-amine compound, primary amine compound or aromatic amine compounds；Preferably, the alcohols
Compound includes methanol, ethyl alcohol or isopropanol；Preferably, the inorganic salts include sulphite, sulfide or nitrite.
7. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that the photochemical catalyst is molten
Molar concentration in liquid B arrives between saturation molar concentration zero, and does not include zero；The halogenated hydrocarbons is mole dense in solution B
Degree arrives between saturation molar concentration zero, and does not include zero；Preferably, molar concentration of the photochemical catalyst in solution B is 5
×10-4M~1 × 10-7M；Preferably, molar concentration of the halogenated hydrocarbons in solution B is 0.001M~10M.
8. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 1, which is characterized in that the light source includes the sun
Light, LED light, medium pressure mercury lamp, high-pressure sodium lamp or xenon lamp.
9. a kind of method of photocatalysis halogenated hydrocarbons dehalogenation conversion and deuterated label, which is characterized in that including as described in claim 1
The step of photocatalysis halogenated hydrocarbons dehalogenation converts；Wherein, the dehalogenation conversion process solvent for use include heavy water or organic solvent and
The mixed solvent of the mixed solvent of heavy water or deuterated organic solvent or deuterated organic solvent and heavy water.
10. the method for photocatalysis halogenated hydrocarbons dehalogenation conversion according to claim 9 and deuterated label, which is characterized in that institute
Stating electronics sacrificial body is selected from the one or more of following compounds: deuterated aminated compounds, deuterated alcohol compound and inorganic
Salt.Preferably, the deuterated aminated compounds includes three-level aminated compounds, secondary-amine compound, primary amine compound or virtue
Fragrant aminated compounds；Preferably, the deuterated alcohol compound includes methanol, ethyl alcohol or isopropanol；Preferably, the inorganic salts
Including sulphite, sulfide or nitrite.
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