CN114716394A - CdS形貌与S空位调节C-H活化构筑惰性化学键 - Google Patents
CdS形貌与S空位调节C-H活化构筑惰性化学键 Download PDFInfo
- Publication number
- CN114716394A CN114716394A CN202210489202.1A CN202210489202A CN114716394A CN 114716394 A CN114716394 A CN 114716394A CN 202210489202 A CN202210489202 A CN 202210489202A CN 114716394 A CN114716394 A CN 114716394A
- Authority
- CN
- China
- Prior art keywords
- cds
- activation
- reaction
- vacancy
- bond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000010499 C–H functionalization reaction Methods 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title claims description 20
- 230000033228 biological regulation Effects 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- 239000002073 nanorod Substances 0.000 claims abstract description 41
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000010287 polarization Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 230000005684 electric field Effects 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 238000006757 chemical reactions by type Methods 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 9
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002077 nanosphere Substances 0.000 claims description 8
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 6
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical compound C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- -1 heterocyclic organic compound Chemical class 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- YFPQIXUNBPQKQR-UHFFFAOYSA-N 1-ethynyl-2-fluorobenzene Chemical group FC1=CC=CC=C1C#C YFPQIXUNBPQKQR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LTLVZQZDXQWLHU-UHFFFAOYSA-N 1-bromo-4-ethynylbenzene Chemical group BrC1=CC=C(C#C)C=C1 LTLVZQZDXQWLHU-UHFFFAOYSA-N 0.000 claims description 2
- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 claims description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical compound CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229940097275 indigo Drugs 0.000 claims description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims 5
- 238000012876 topography Methods 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 103
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 68
- 239000000047 product Substances 0.000 description 29
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 18
- 239000000725 suspension Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 238000013032 photocatalytic reaction Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- XIXWTBLGKIRXOP-UHFFFAOYSA-N 2-ethenyloxolane Chemical compound C=CC1CCCO1 XIXWTBLGKIRXOP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 101150060950 CD3D gene Proteins 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UFOVULIWACVAAC-UHFFFAOYSA-N 1-ethynyl-2-methoxybenzene Chemical group COC1=CC=CC=C1C#C UFOVULIWACVAAC-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- MYBSUWNEMXUTAX-UHFFFAOYSA-N 1-ethynyl-2-methylbenzene Chemical group CC1=CC=CC=C1C#C MYBSUWNEMXUTAX-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IAWCIZWLKMTPLL-UHFFFAOYSA-N fluoroethyne Chemical group FC#C IAWCIZWLKMTPLL-UHFFFAOYSA-N 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种基于CdS形貌与S空位调节C‑H活化构筑C‑C/C‑N/C‑S键的多相光催化方法，通过制备具有S空位的六方相CdS纳米棒（Sv‑CdS NRs）作为光催化剂，并将催化剂用于C‑H活化构筑C‑C/C‑N/C‑S键以制备2‑乙烯基杂环衍生物等药物中间体或其他精细化学品。Sv‑CdS NRs在无碱性添加剂和氧化剂的存在下，对THF的C‑H活化转化为2‑乙烯基杂环衍生物并附带产氢的反应过程中具有优秀的活性与选择性。Sv‑CdS NRs优秀的光催化性能归因于S空位带来的更多活性位点以及六方晶相所诱导的晶格畸变产生的极化偶极矩和内化电场，这有效地促进了光生电子和空穴的分离。同时，Sv‑CdS NRs在其他的C‑H活化构筑C‑C/C‑N/C‑S键反应类型中均有不错的表现。该催化剂制备方法简单易操作，可用于高效光催化C‑H活化构筑C‑C/C‑N/C‑S键，反应条件温和，催化剂稳定性好且易回收利用。
Description
技术领域
本发明涉及CdS形貌与S空位调节C-H活化构筑惰性化学键。
背景技术
C-H键的直接活化是有机合成领域的重要研究内容，对发展医药中间体和精细化学品的绿色合成具有重要意义。然而，在许多有效的C-H键选择性转化反应中，只有负载贵金属或复杂的反应条件才能获得优异的产率。因此，如何在温和的条件下实现C-H键的选择性转化，尤其是sp3 C-H键的选择性转化，已成为有机合成领域的一大难题。同时，在许多多相催化反应体系中，仍然存在着反应温度高、反应条件苛刻等问题，如何温和简洁地激活C-H键来构建C-X（X=C，N，S）化学键受到研究者的广泛关注。
在多相光催化系统中，将高附加值产品合成和制氢相结合已成为实现可持续发展的一个有趣途径。显然，在多相光催化下构建含有高原子经济性的精细化学品/医药中间体的C-C/C-N/C-S键仍然是一项相当具有挑战性的任务。金属硫化物被认为是多相光催化体系中很好的候选者，其中硫化镉（CdS）由于其窄带隙、合适的能带结构和比H+/H2氧化还原电位更负的导带边缘位置，在污染物降解、CO2转化和精细化学品合成方面得到了广泛的探索。但由于其光腐蚀性严重，因此对于如何将CdS高效应用于多相光催化体系中还亟需进一步发展。
发明内容
本发明提供了一种具有S空位的六方相CdS纳米棒光催化剂的制备及C-H活化构筑C-C/C-N/C-S键的多相光催化方法。在无碱性添加剂和氧化剂的条件下，具有S空位的六方相CdS纳米棒(Sv-CdS NRs)对四氢呋喃的C-H活化转化为2-乙烯基杂环衍生物以及附带产氢具有优秀的活性与选择性；同时，Sv-CdS NRs在其他的C-H活化构筑C-C/C-N/C-S键及产氢反应类型中均有不错的表现，这可归因于Sv-CdS NRs S空位带来的更多活性位点以及六方晶相所诱导的晶格畸变产生的极化偶极矩和内化电场，这有效地提高了光生电子和空穴的分离效率。
本发明提供CdS形貌与S空位调节C-H活化构筑惰性化学键，该催化剂制备方法简单易操作，可用于光催化高效激活C-H键构筑C-C/C-N/C-S键，反应条件温和，催化剂容易回收利用。
为了实现上述目的，本发明采用以下技术方案：
具有S空位的六方相CdS纳米棒光催化剂的制备方法，所述制备方法包括以下步骤：
(1)2.0 mmol Cd（OAc）2·2H2O和6.0 mmol硫脲分散在60 mL乙二胺中，然后转移到聚四氟乙烯内衬的不锈钢高压釜（100 mL）中，在100℃下加热8 h，反应后，分离亮黄色产物，并用去离子水和乙醇洗涤几次，然后在真空烘箱中干燥获得CdS纳米片。
(2)将0.6 mmol Cd（OAc）2·2H2O和15 mmol硫脲溶解在15 mL去离子水中，形成均相溶液，然后将混合物转移到聚四氟乙烯内衬的不锈钢高压釜(80ml)中，在140℃下加热并保持5小时。通过离心获得固体，并用去离子水和乙醇洗涤几次，然后进行冷冻干燥处理获得CdS纳米球。
(3)在180℃的固定反应温度下，通过溶剂热反应制备CdS纳米棒。将硝酸镉（1.92g）和硫脲（1.42 g）溶解在乙二胺中并搅拌15分钟，将透明溶液转移到100 mL聚四氟乙烯内衬的不锈钢高压釜中，并在180℃下加热18小时。冷却至室温后，用乙醇和去离子水多次洗涤黄色沉淀物，并在70℃下干燥过夜获得CdS纳米棒。
(4)将获得的CdS纳米棒用作前体，并将其置于管式炉中，在氮气保护下以10℃/min的加热速率加热至800℃，并保持30分钟以获得具有S空位的六方相CdS纳米棒Sv-CdSNRs。
一种具有S空位的六方相CdS纳米棒光催化剂的制备及C-H活化构筑C-C/C-N/C-S键的多相光催化方法，包括步骤：
将具有S空位的六方相CdS纳米棒光催化剂Sv-CdS NRs放置在配有氩气球的玻璃反应器中，加入苯乙炔和四氢呋喃。在0.75 W/cm2蓝色LED（460 nm）照射下反应24 h，通过GC和GC-MS分析2-乙烯基杂环衍生物的转化率和产物选择性。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：在无光照时无催化活性，在光促进下催化活性较高。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：所采用光照颜色可为红、橙、黄、绿、蓝、靛、紫中的一种或几种混合光，催化剂经过五次循环后依旧保持良好的光催化活性且容易回收利用。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：在无形貌调控和S空位引入时具有一定的催化活性；在形成六方相CdS纳米棒结构和S空位引入后反应催化活性大幅度提高。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：所述的杂环有机化合物包括：四氢呋喃、1,3-二氧五环、1,4-二氧六环、吡喃；所述的芳香族化合物包括：苯乙炔、2-氟苯乙炔、4-氯苯乙炔、4-溴苯乙炔、4-乙炔基甲苯、2-乙炔基吡啶、4-甲氧基苯乙炔、苯乙烯、4-甲基苯乙烯。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：所述的构筑C-C/C-N/C/S键的底物包括：N,N-二甲基甲酰胺、甲苯、苄胺、苄硫醇、乙基苯。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：Sv-CdS NRs优秀的光催化性能归因于S空位带来的更多活性位点以及六方晶相所诱导的晶格畸变引起的极化偶极矩和内化电场，这有效地提高了光生电子和空穴的分离效率。
上述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：催化体系中所采用的氩气或者二氧化碳压力为加压或1 atm。
说明书附图
图1是实施案例1制备CdS纳米片（图1a），CdS纳米球（图1b），CdS纳米棒（图1c）的SEM图。
图2是实施案例1制备的CdS纳米棒（图2a）和Sv-CdS NRs（图2c）的透射电镜图（transmission electron microscope，TEM）、以及CdS纳米棒（图2b）的高倍透射电镜图（High Resolution Transmission Electron Microscope，HRTEM）。
图3是实施案例1制备的CdS纳米片，CdS纳米棒，CdS纳米球，Sv-CdS NRs催化剂的X射线衍射图谱（X-ray diffraction，XRD）。
图4是实施案例1制备的CdS纳米棒和Sv-CdS NRs的S和Cd的X射线光电子能谱（X-ray photoelectron spectroscopy，XPS）图。总谱（图4a）,S 2p谱图（图4b）,Cd 3d谱图（图4c）。
具体实施方式
下面结合具体实施案例对本发明进行详细说明。
实施案例1：
光催化剂制备包括以下步骤：
1）2.0 mmol Cd（OAc）2·2H2O和6.0 mmol硫脲分散在60 mL乙二胺中，然后转移到聚四氟乙烯内衬的不锈钢高压釜（100 mL）中，在100℃下加热8 h，反应后，分离亮黄色产物，并用去离子水和乙醇洗涤几次，然后在真空烘箱中干燥获得CdS纳米片。
2）将0.6 mmol Cd（OAc）2·2H2O和15 mmol硫脲溶解在15 mL去离子水中，形成均相溶液。然后将混合物转移到聚四氟乙烯内衬的不锈钢高压釜(80ml)中，在140℃下加热并保持5小时，通过离心获得固体，并用去离子水和乙醇洗涤几次，然后进行冷冻干燥处理获得CdS纳米球。
3）在180℃的固定反应温度下，通过溶剂热反应制备CdS纳米棒。将硝酸镉（1.92g）和硫脲（1.42 g）溶解在乙二胺中并搅拌15分钟，将透明溶液转移到100 mL聚四氟乙烯内衬的不锈钢高压釜中，并在180℃下加热18小时，冷却至室温后，用乙醇和去离子水多次洗涤黄色沉淀物，并在70℃下干燥过夜获得CdS纳米棒。
4）将获得的CdS纳米棒用作前体，并将其置于管式炉中，在氮气保护下以10℃/min的加热速率加热至800℃，并保持30分钟以获得具有S空位的六方相CdS纳米棒Sv-CdS NRs。
图1是上述步骤1）、2）以及3）合成的CdS纳米片，CdS纳米球和CdS纳米棒的SEM图，从图中可以明显看出，CdS纳米片显示了许多薄片堆叠在一起的典型结构（图1a），导致催化材料相对高度的聚集，这可能会阻碍光生载流子向活性表面的迁移，并导致电荷复合。在图1b中，CdS纳米球由直径在40到60纳米之间的均匀颗粒组成。同时CdS纳米棒具有均匀和笔直的一维形貌，且直径约为50 nm（图1c）。
图2是使用透射电子显微镜（TEM）表征了CdS纳米棒及Sv-CdS NRs的微观结构，并观察到规则形状的CdS纳米棒（图2a）。纳米棒的形貌特征提供了较大的长宽比，改善了光的吸收和利用，并使光生载流子易于迁移到表面活性中心，这有利于光催化。此外，HRTEM图像显示了晶面间距（d=0.318 nm）的明显晶格条纹，这与六方相CdS（101）面相对应（图2b）。煅烧处理后，Sv-CdS NRs的棒状形状得以保持，但其边缘变得略微不规则，如图2c所示。这可能是由于高温煅烧破坏了纳米材料边缘的基本单元结构，导致边缘结构坍塌。
图3是实施案例1制备催化剂CdS纳米片，CdS纳米球、CdS纳米棒以及Sv-CdS NRs的XRD图谱。如图所示，所有CdS样品的衍射图显示出相似的特征。且衍射峰均对应于CdS六方晶相。（002）晶面作为CdS的高能活性晶面出现在所有CdS样品中。通过煅烧引入S空位的Sv-CdS NRs具有最佳的结晶度，并且（100）、（101）和（102）晶面的衍射峰有一定程度的增强。这是因为CdS纳米棒在高温下更容易形成六方相，这导致六方相的特征晶面高度暴露。同时，这表明Sv-CdS纳米棒具有更强的六方相特性，意味着纳米棒内部存在更严重的晶格畸变，导致极化偶极矩和内部极化电场，促进了光生载流子的分离和扩散。
图4是上述3）和4）所制备的CdS纳米棒和Sv-CdS NRs的XPS图:a）全谱，b) S 2p,c) Cd3d。如测试谱图（图4a）所示，S和Cd的信号峰共存于CdS纳米棒和Sv-CdS NRs中。在图4b中，Sv CdS的S 2p3/2和2p1/2分别为160.71eV和161.84eV。在引入S空位后，CdS纳米棒检测到明显的S 2p3/2和2p1/2负位移，分别为0.15eV和0.17eV。这是由于S空位具有较强的电子吸收能力，随着CdS纳米棒中电子向S空位转移，S原子平衡电子云密度降低。因此，S空位形成后会导致S原子的结合能降低。Sv-CdS催化剂的Cd 3d高分辨率光谱可以反褶积为两个主峰，分别约为404.98eV和411.78eV（图4c），它们被指定为Sv-CdS中Cd2+的Cd 3d5/2和Cd3d3/2。值得注意的是，在Sv-CdS中观察到Cd 3d结合能的某些负位移（约0.19 eV），这应该解释为CdS之间的键极性将通过改变表面S原子缺失引起的化学环境来调整。与S2-峰相比，Cd2+的XPS峰的更大位移可能是由于金属峰比非金属峰对化学环境更敏感。
实施案例2（反应参考表1，条目1）
将CdS纳米棒（10 mg）和苯乙炔（0.2 mmol）放置在含有四氢呋喃（5 ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）的照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。通过GC和GC-MS进行分析2-乙烯基四氢呋喃的转化率为83%。
实施案例3（反应参考表1，条目6）
将CdS纳米棒（10 mg）、苯乙炔（0.2 mmol）和K2CO3（20mg）放置在含有四氢呋喃（5ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）的照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。通过GC和GC-MS进行分析2-乙烯基四氢呋喃的转化率为41%。
实施案例4（反应参考表1，条目7）
将CdS纳米棒（10 mg）、苯乙炔（0.2 mmol）和Cs2CO3（20mg）放置在含有四氢呋喃（5ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）的照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。通过GC和GC-MS进行分析2-乙烯基四氢呋喃的转化率为30%。
实施案例5（反应参考表1，条目9）
将CdS纳米棒（10 mg）、苯乙炔（0.2 mmol）和2-甲基吡啶（20mg）放置在含有四氢呋喃（5 ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）的照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。通过GC和GC-MS进行分析2-乙烯基四氢呋喃的转化率为77%。
实施案例6（反应参考表1，条目11）
将CdS纳米片（10 mg）、苯乙炔（0.2 mmol）放置在含有四氢呋喃（5 ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）的照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。通过GC和GC-MS进行分析2-乙烯基四氢呋喃的转化率为64%。
实施案例7（反应参考表1，条目12）
将Sv-CdS NRs（10 mg）、苯乙炔（0.2 mmol）放置在含有四氢呋喃（5 ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）的照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。通过GC和GC-MS进行分析2-乙烯基四氢呋喃的转化率为95%。
实施案例8（反应参考表2，3b）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol苯乙炔和5 mL的1,3-二氧五环，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析苯乙炔的转化率和产物选择性。苯乙炔的转化率为53%，对应的顺反异构产物选择性为E/Z=0.7。
实施案例9（反应参考表2，3e）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol的2-氟苯乙炔和5 mL四氢呋喃，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析2-氟苯乙炔的转化率和产物选择性。2-氟苯乙炔的转化率为68%，对应的顺反异构产物选择性为E/Z=2.2。
实施案例10（反应参考表2，3j）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol的2-甲氧基苯乙炔和5 mL四氢呋喃，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析2-甲氧基苯乙炔的转化率和产物选择性。2-甲氧基苯乙炔的转化率为87%，对应的顺反异构产物选择性为E/Z=4.6。
实施案例11（反应参考表2，3m）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol的2-甲基苯乙炔和5 mL四氢呋喃，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析2-甲基苯乙炔的转化率和产物选择性。2-甲基苯乙炔的转化率为78%，对应的顺反异构产物选择性为E/Z=2.2。
实施案例12（反应参考表2，3p）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol的2-乙炔基吡啶和5 mL四氢呋喃，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析2-乙炔基吡啶的转化率和产物选择性。2-乙炔基吡啶的转化率为87%，对应的顺反异构产物选择性为E/Z=0.6。
实施案例13（反应参考表2，5a）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol苯乙烯和5 mL四氢呋喃，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析苯乙烯的转化率。苯乙烯的转化率为89%。
实施案例14（反应参考表2，5f）
将10 mg 制备的Sv-CdS NRs置于密闭玻璃反应器中，使用氩气多次置换管内空气后，配备充满氩气的气球，加入0.2 mmol4-甲基苯乙烯和5 mL四氢呋喃，在0.75 W/cm2蓝色LED灯照射下反应24 h，通过GC和GC-MS分析4-甲基苯乙烯的转化率。4-甲基苯乙烯的转化率为63%。
实施案例15（反应参考表3，条目1）
DMF与苯乙烯的光催化反应：将Sv-CdS NRs（10 mg）和20mg碱性添加剂Cs2CO3添加到Schlenk管中，该管充满N2以去除O2。然后，向Schlenk管中加入0.2 mmol苯乙烯和4 mLDMF。在0.75 W/cm2蓝色LED（460 nm）下搅拌混合物24小时。反应后，通过多孔膜（直径20μm）过滤混合物，并通过HPLC进行分析，测得偶联产物产率为87%。气体产物用TCD检测器进行GC分析,检测到氢气产生。
实施案例16（反应参考表3，条目2）
DMF与4-甲基苯乙烯的光催化反应：将Sv-CdS NRs（10 mg）和20mg碱性添加剂Cs2CO3添加到Schlenk管中，该管充满N2以去除O2。然后，向Schlenk管中加入0.2 mmol 4-甲基苯乙烯和4 mL DMF。在0.75 W/cm2蓝色LED（460 nm）下搅拌混合物24小时。反应后，通过多孔膜（直径20μm）过滤混合物，并通过HPLC进行分析，测得偶联产物产率为91%。气体产物用TCD检测器进行GC分析,检测到氢气产生。
实施案例17（反应参考表3，条目3）
甲苯与苯乙烯的光催化反应：将Sv-CdS NRs（10 mg）和苯乙烯（0.2mmol）置于含有甲苯（2ml）和二氯甲烷（2ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.75 W/cm2蓝色LED（460 nm）照射下进行24小时，并在整个反应过程中持续搅拌反应悬浮液。反应后，通过GC和GC-MS分析滤液，测得偶联产物产率为73%。气体产物用TCD检测器进行GC分析,检测到氢气产生。
实施案例18（反应参考表3，条目4）
苄胺自偶联的光催化反应：将Sv-CdS NRs（10 mg）和苄胺（0.5mmol）置于含有乙腈（2ml）的Schlenk管中。在反应之前，将悬浮液脱气并用Ar饱和，以去除任何溶解的O2。反应在0.15 W/cm2蓝色LED（460 nm）照射下进行12小时，并在整个反应过程中持续搅拌反应悬浮液。反应后，通过GC和GC-MS分析滤液，测得偶联产物产率为82%。
实施案例19（反应参考表3，条目5）
苄硫醇与苯乙炔的光催化反应：Sv-CdS NRs（10 mg）、苄硫醇（0.1 mmol）和苯乙炔（0.12 mmol）悬浮在含有甲醇溶剂（4 ml）的Schlenk管中。在反应之前，将悬浮液脱气并用N2饱和，以去除任何溶解的O2。反应在室温下用0.75 W/cm2蓝色LED（460 nm）照射下进行。反应后，使用GC和GC-MS对产物进行分析，测得偶联产物产率为83%。气体产物用TCD检测器进行GC分析,检测到氢气产生。
实施案例20（反应参考表3，条目6）
苄硫醇与苯乙烯的光催化反应：Sv-CdS NRs（10 mg）、苄硫醇（0.1 mmol）和苯乙烯（0.12 mmol）悬浮在含有甲醇溶剂（4 ml）的Schlenk管中。在反应之前，将悬浮液脱气并用N2饱和，以去除任何溶解的O2。反应在室温下用0.75 W/cm2蓝色LED（460 nm）照射下进行。反应后，使用GC和GC-MS对产物进行分析，测得偶联产物产率为76%。气体产物用TCD检测器进行GC分析,检测到氢气产生。
实施案例21（反应参考表3，条目7）
CO2羧化的光催化反应：将Sv-CdS NRs（10 mg)光催化剂和0.3mmol碱添加剂K2CO3添加到充满CO2的Schlenk管中。然后，向Schlenk管中加入0.2 mmol乙苯和5 mL去离子水。在0.75 W/cm2蓝色LED（460 nm）下搅拌混合物24小时。通过多孔膜过滤混合物。酸化后用HPLC分析滤液，测得羧化产物产率为80%。
实施案例22（反应参考表3，条目8）
CO2羧化的光催化反应：将Sv-CdS NRs（10 mg)光催化剂和0.3mmol碱添加剂K2CO3添加到充满CO2的Schlenk管中。然后，向Schlenk管中加入0.2 mmol苯和5 mL去离子水。在0.75 W/cm2蓝色LED（460 nm）下搅拌混合物24小时。通过多孔膜过滤混合物。酸化后用HPLC分析滤液，测得羧化产物产率为90%。
Claims (8)
1.CdS形貌与S空位调节C-H活化构筑惰性化学键，催化材料制备方法为：以乙二胺作为协调剂溶剂热法制备CdS纳米棒、CdS纳米片以及CdS纳米球，在800℃对CdS纳米棒进行煅烧30分钟制备具有S空位的六方相CdS纳米棒（Sv-CdS NRs），光催化高效C-H活化构筑C-C/C-N/C-S键的方法包括：在无碱性添加剂和氧化剂的存在下，光催化剂对四氢呋喃的C-H活化转化为2-乙烯基杂环衍生物以及附带产氢具有优秀的活性与选择性，Sv-CdS NRs优秀的光催化性能归因于S空位带来的更多活性位点以及六方晶相所诱导的晶格畸变产生的极化偶极矩和内化电场，这有效地提高了光生电子和空穴的分离效率，同时，Sv-CdS NRs在其他的C-H活化构筑C-C/C-N/C-S键反应类型中均有不错的表现。
2.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：在无光照时无催化活性，在光促进下催化活性较高。
3.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：所采用光照颜色可为红、橙、黄、绿、蓝、靛、紫中的一种或几种混合光，催化剂经过五次循环后依旧保持良好的光催化活性且容易回收利用。
4.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：在无形貌调控和S空位引入时具有一定的催化活性；在形成六方相CdS纳米棒结构和S空位引入后反应催化活性大幅度提高。
5.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键其特征在于：在无碱性添加剂和氧化剂条件下，催化反应也可以高效的转化率进行。
6.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：所述的杂环有机化合物包括：四氢呋喃、1,3-二氧五环、1,4-二氧六环、吡喃，所述的芳香族化合物包括：苯乙炔、2-氟苯乙炔、4-氯苯乙炔、4-溴苯乙炔、4-乙炔基甲苯、2-乙炔基吡啶、4-甲氧基苯乙炔、苯乙烯、4-甲基苯乙烯。
7.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：所述的构筑C-C/C-N/C/S键的化合物包括：N,N-二甲基甲酰胺、甲苯、苄胺、苄硫醇、乙基苯。
8.根据权利要求1所述的CdS形貌与S空位调节C-H活化构筑惰性化学键，其特征在于：催化体系中所采用的氩气或者二氧化碳压力为加压或1 atm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210489202.1A CN114716394B (zh) | 2022-05-07 | 2022-05-07 | CdS形貌与S空位调节C-H活化构筑惰性化学键 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210489202.1A CN114716394B (zh) | 2022-05-07 | 2022-05-07 | CdS形貌与S空位调节C-H活化构筑惰性化学键 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114716394A true CN114716394A (zh) | 2022-07-08 |
| CN114716394B CN114716394B (zh) | 2023-07-28 |
Family
ID=82231474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210489202.1A Active CN114716394B (zh) | 2022-05-07 | 2022-05-07 | CdS形貌与S空位调节C-H活化构筑惰性化学键 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114716394B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116618064A (zh) * | 2023-05-23 | 2023-08-22 | 江西省科学院能源研究所 | 一种光致缺陷的CdS纳米片光催化剂制备方法及其在氢硅烷与醇类脱氢偶联反应中的应用 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357424A (zh) * | 2013-07-26 | 2013-10-23 | 福州大学 | 一种用于甲苯及其衍生物选择性氧化的光催化剂 |
| IN2013MU02993A (zh) * | 2013-09-16 | 2015-07-03 | Secretary Dept Of Electronics And Information Technology Deity | |
| CN107649150A (zh) * | 2017-09-28 | 2018-02-02 | 福州大学 | 一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用 |
| CN111715262A (zh) * | 2020-07-03 | 2020-09-29 | 重庆工商大学 | 负载钯金富氮类氮化碳光催化剂的制备及c-c键合成 |
| CN112619668A (zh) * | 2020-12-25 | 2021-04-09 | 安徽工业大学 | 一种光催化用CdS@SnS2复合材料及其制备方法和应用 |
| CN113145138A (zh) * | 2021-03-11 | 2021-07-23 | 福州大学 | 热响应型复合光催化剂及其制备方法和应用 |
| CN113578395A (zh) * | 2021-07-02 | 2021-11-02 | 重庆工商大学 | Pd/Fe-MOFs促进光催化C-N和C-C键合成 |
| CN114029071A (zh) * | 2021-11-18 | 2022-02-11 | 青岛科技大学 | 一种兼具B掺杂和S空位及肖特基结的B-ZCSv/Cd和制备方法并用于染料废水产氢 |
-
2022
- 2022-05-07 CN CN202210489202.1A patent/CN114716394B/zh active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357424A (zh) * | 2013-07-26 | 2013-10-23 | 福州大学 | 一种用于甲苯及其衍生物选择性氧化的光催化剂 |
| IN2013MU02993A (zh) * | 2013-09-16 | 2015-07-03 | Secretary Dept Of Electronics And Information Technology Deity | |
| CN107649150A (zh) * | 2017-09-28 | 2018-02-02 | 福州大学 | 一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用 |
| CN111715262A (zh) * | 2020-07-03 | 2020-09-29 | 重庆工商大学 | 负载钯金富氮类氮化碳光催化剂的制备及c-c键合成 |
| CN112619668A (zh) * | 2020-12-25 | 2021-04-09 | 安徽工业大学 | 一种光催化用CdS@SnS2复合材料及其制备方法和应用 |
| CN113145138A (zh) * | 2021-03-11 | 2021-07-23 | 福州大学 | 热响应型复合光催化剂及其制备方法和应用 |
| CN113578395A (zh) * | 2021-07-02 | 2021-11-02 | 重庆工商大学 | Pd/Fe-MOFs促进光催化C-N和C-C键合成 |
| CN114029071A (zh) * | 2021-11-18 | 2022-02-11 | 青岛科技大学 | 一种兼具B掺杂和S空位及肖特基结的B-ZCSv/Cd和制备方法并用于染料废水产氢 |
Non-Patent Citations (6)
| Title |
|---|
| VIKRAM U. PANDIT,等: "Hierarchical CdS nanostructure by Lawesson\'s reagent and its enhanced photocatalytic hydrogen production", RSC ADVANCES, vol. 05, pages 13715 - 13721 * |
| ZUJIE HU,等: "Photocatalytic C–H activation for C–C/C[double bond, length as m-dash]N/C–S bond formation over CdS: effect of morphological regulation and S vacancies", CATALYSIS SCIENCE & TECHNOLOGY, vol. 12, pages 6728 - 6739 * |
| 张钦峰;等: "微波水热法制备CdS单分散纳米球及其形貌控制", 无机化学学报, vol. 29, no. 02, pages 271 - 276 * |
| 张鹏,等: "水热微乳液法合成硫化镉纳米棒晶", 无机材料学报, no. 04, pages 772 - 776 * |
| 白雪峰;等: "硫化镉的改性方法及其在光催化反应中的应用", 太阳能学报, vol. 29, no. 09, pages 1117 - 1123 * |
| 赵平堂;等: "溶剂热法制备纳米线组成的片状硫化镉纳米结构", 河南科技, no. 21, pages 87 - 89 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116618064A (zh) * | 2023-05-23 | 2023-08-22 | 江西省科学院能源研究所 | 一种光致缺陷的CdS纳米片光催化剂制备方法及其在氢硅烷与醇类脱氢偶联反应中的应用 |
| CN116618064B (zh) * | 2023-05-23 | 2024-01-23 | 江西省科学院能源研究所 | 一种光致缺陷的CdS纳米片光催化剂制备方法及其在氢硅烷与醇类脱氢偶联反应中的应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114716394B (zh) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Selective aerobic oxidation of biomass-derived HMF to 2, 5-diformylfuran using a MOF-derived magnetic hollow Fe–Co nanocatalyst | |
| Guo et al. | Synthesis of core–shell ZIF-67@ Co-MOF-74 catalyst with controllable shell thickness and enhanced photocatalytic activity for visible light-driven water oxidation | |
| Zhou et al. | P, S Co-doped g-C3N4 isotype heterojunction composites for high-efficiency photocatalytic H2 evolution | |
| Zhang et al. | Palladium nanoparticle supported on metal–organic framework derived N-decorated nanoporous carbon as an efficient catalyst for the Suzuki coupling reaction | |
| CN105772049B (zh) | 一种用于合成气直接制备烯烃的碳化钴基催化剂及其制备方法和应用 | |
| Dong et al. | Palladium nanoparticles embedded in metal–organic framework derived porous carbon: synthesis and application for efficient Suzuki–Miyaura coupling reactions | |
| Pei et al. | Size-controllable ultrafine palladium nanoparticles immobilized on calcined chitin microspheres as efficient and recyclable catalysts for hydrogenation | |
| CN114736179B (zh) | ZnIn2S4纳米片光催化C-H活化和CO2还原 | |
| Sadeghzadeh | PbS based ionic liquid immobilized onto fibrous nano-silica as robust and recyclable heterogeneous catalysts for the hydrogen production by dehydrogenation of formic acid | |
| Qiu et al. | Photocatalytic conversion of sodium lignosulfonate into vanillin using mesoporous TiO2 derived from MIL-125 | |
| CN110756203A (zh) | 一种Ni2P/Mn0.3Cd0.7S光催化分解水复合催化剂及其制备方法与应用 | |
| CN112844476A (zh) | 一种生物质基碳材料负载纳米镍催化剂及其制备方法和应用 | |
| He et al. | Promoting photothermal catalytic CO2 reduction of Cd2In2S5/Cd0. 3Zn0. 7S heterojunction with encapsulated hydrogen evolution active site by accelerating charge transfer kinetics | |
| Zhang et al. | One-step synthesis of mesoporous Pt–Nb 2 O 5 nanocomposites with enhanced photocatalytic hydrogen production activity | |
| Song et al. | Vopor-polymerization strategy to carbon-rich holey few-layer carbon nitride nanosheets with large domain size for superior photocatalytic hydrogen evolution | |
| CN114716394A (zh) | CdS形貌与S空位调节C-H活化构筑惰性化学键 | |
| Zhang et al. | N-Doped porous carbon supported palladium nanoparticles as a highly efficient and recyclable catalyst for the Suzuki coupling reaction | |
| CN109876815B (zh) | 石墨烯/ZnFe2O4复合可见光催化剂及其制备方法 | |
| CN114849785A (zh) | 一种三嗪环共价有机框架材料掺杂卟啉钴光催化剂的制备 | |
| CN113120977B (zh) | 由含镍铁电镀废水制备铁酸镍纳米材料的方法及应用 | |
| CN108948366B (zh) | 一种具有丰富Lewis酸性位的Fe-MOF催化剂的制备及其脱硫应用 | |
| CN114797928B (zh) | 一种核壳ZIFs热解衍生的多孔碳材料钴催化剂及其制备方法 | |
| Premi et al. | A nitrogen and sulphur functionalized graphene oxide–palladium nanoparticle hybrid catalyst for an efficient Heck coupling | |
| CN113546687A (zh) | 一种超薄钛基MOFs纳米片的可见光催化剂的制备方法及应用 | |
| Roongraung et al. | CdS/TiO 2 nanostructures synthesized via the SILAR method for enhanced photocatalytic glucose conversion and simultaneous hydrogen production under UV and simulated solar irradiation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |