CN112354551A - Novel monoatomic metal photocatalyst, preparation method thereof and application thereof in carbon-oxygen cross-coupling reaction - Google Patents
Novel monoatomic metal photocatalyst, preparation method thereof and application thereof in carbon-oxygen cross-coupling reaction Download PDFInfo
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- CN112354551A CN112354551A CN202011270835.0A CN202011270835A CN112354551A CN 112354551 A CN112354551 A CN 112354551A CN 202011270835 A CN202011270835 A CN 202011270835A CN 112354551 A CN112354551 A CN 112354551A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims description 17
- 238000006880 cross-coupling reaction Methods 0.000 title claims description 7
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000003960 organic solvent Chemical class 0.000 claims description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- JYAQYXOVOHJRCS-UHFFFAOYSA-N 1-(3-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=C1 JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 claims description 2
- XLQSXGGDTHANLN-UHFFFAOYSA-N 1-bromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C=C1 XLQSXGGDTHANLN-UHFFFAOYSA-N 0.000 claims description 2
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 claims description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 2
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 claims description 2
- DMSHUVBQFSNBBL-UHFFFAOYSA-N 5-bromopyridine-2-carbonitrile Chemical compound BrC1=CC=C(C#N)N=C1 DMSHUVBQFSNBBL-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- XZIAFENWXIQIKR-UHFFFAOYSA-N ethyl 4-bromobenzoate Chemical compound CCOC(=O)C1=CC=C(Br)C=C1 XZIAFENWXIQIKR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 125000000075 primary alcohol group Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 2
- 150000002170 ethers Chemical class 0.000 claims 2
- 150000002989 phenols Chemical class 0.000 claims 2
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
The invention belongs to the field of photocatalysis/metal catalysis organic synthesis, and provides a carbon-based single-atom metal catalytic material, a preparation method and application thereof. The catalyst comprises a graphite type carbon nitride substrate, a metal center and a sheet form with uniformly distributed metal atoms, wherein the metal is anchored on the surface of the substrate in the form of ions. The catalyst developed by the invention has the advantages of low reaction temperature, high conversion rate, wide applicable substrate range, less side reaction and the like, and particularly has obvious advantages compared with the existing catalyst in the aspects of conversion number, metal utilization efficiency, preparation cost and recycling.
Description
Technical Field
The invention relates to the field of photo/metal catalytic synthesis, in particular to the research and development of a novel monatomic metal photocatalyst for synthesizing ether/phenol by cross carbon-oxygen coupling.
Background
The cross coupling reaction of carbon, oxygen, carbon and nitrogen is an important reaction for preparing medicines and fine chemical products. The traditional catalyst mainly comprises a metal palladium complex, and the ligand structure is complex; in addition, strong organic bases such as potassium tert-butoxide and the like are required or the reaction is completed by raising the temperature. An important breakthrough in the catalytic system for the heterocoupling reaction in recent years is the realization of the coupling reaction driven by light by combining photocatalysis and metal catalysis. The photocatalyst can be selected from molecular dye or semiconductor material, the first transition metal complex is used for replacing noble metal palladium, the ligand structure is relatively simple, and strong base assistance is not needed. The core reaction step is that photoinduced electron or energy transfer triggers the change of metal valence state, thereby giving the coupling product through oxidative addition-reduction elimination. The electron or energy transfer efficiency in the initiation step is limited, the speed of the light-driven coupling reaction needs to be further improved, and in addition, higher metal complex dosage is usually required in the reaction, so that the problems of metal deposition inactivation, poor cyclic utilization rate and the like exist.
Disclosure of Invention
The invention provides a monoatomic metal photocatalytic material, which is in a lamellar form with uniformly distributed metal atoms; the metal is ionically supported on the substrate surface and the metal loading may be 0.04 to 0.36 wt%, for example 0.1 to 0.2 wt%, illustratively 0.11 wt%.
According to an embodiment of the present invention, the method for preparing the monatomic metallic photocatalytic material includes the steps of:
step (1): heating and calcining the small-molecule precursor by a program to obtain a graphite type carbon nitride substrate;
step (2): and (2) dispersing the substrate in the step (1) in a polar organic solution of metal salt, and reacting to obtain the monatomic metal photocatalytic material.
According to an embodiment of the present invention, the small molecule precursor in step (1) may be at least one selected from urea, cyanamide, dicyandiamide, melamine;
according to an embodiment of the invention, in step (1), the calcination is preferably carried out in a muffle furnace; the calcination time may be 1-5h, e.g. 2h, and the temperature rise rate is 1-5 deg.C/min, e.g. 2 deg.C/min.
According to an embodiment of the present invention, step (1) further comprises the steps of washing and drying the substrate after the calcination; the cleaning step is that ethanol and water are used for cleaning for a plurality of times in sequence; the drying time may be 2-24h, for example 12 h.
According to an embodiment of the present invention, in the step (2), the metal salt may be a nickel salt, such as nickel chloride, nickel nitrate, nickel sulfate, tetrasodium salt of nitinol tetrasulfonic acid, or respective hydrates thereof;
according to an embodiment of the present invention, in the step (2), the polar organic solvent may be selected from at least one of dimethylformamide, dimethylacetamide, N-dimethylformamide dimethyl acetal, or dimethylsulfoxide;
according to an embodiment of the present invention, in the step (2), the mass ratio of the metal salt to the substrate may be (1-60):500, for example (20-60): 500.
According to an embodiment of the invention, in step (2), the concentration of the metal salt in the polar organic solvent may be from 0.02 to 5mmol/L, for example from 0.05 to 2mmol/L, exemplarily 1 mmol/L;
according to an embodiment of the invention, in step (2), the concentration of the substrate in the polar organic solvent is 1-5g/L, such as 2 g/L.
According to an embodiment of the invention, in step (2), the reaction time may be 1 to 12h, for example 6 h;
according to an embodiment of the present invention, the step (2), after the reaction, further comprises washing with a reaction solvent at least twice; after washing, drying is carried out for 2 to 24 hours, for example 12 hours.
The invention also provides application of the monatomic metal photocatalytic material as a photocatalyst.
The invention also provides a photocatalyst which comprises the monatomic metal photocatalytic material.
The invention also provides a catalyst composition comprising the photocatalyst and an ancillary ligand.
According to an embodiment of the present invention, the ancillary ligand may be an azaaryl compound, for example, at least one selected from the group consisting of pyridine, imidazole, aminoimidazole, bipyridine, pyrrole, pyrazole, and pyrimidine;
the invention also provides application of the photocatalyst and/or the catalyst composition in carbon-oxygen cross-coupling reaction, such as application in catalyzing reaction of halogenated hydrocarbon and alcohol to prepare ether or phenol.
According to an embodiment of the present invention, the halogenated hydrocarbon may be a halogenated aromatic compound, such as p-bromoacetophenone, p-bromotrifluorotoluene, p-bromobenzonitrile, p-bromobenzaldehyde, ethyl p-bromobenzoate, m-bromoacetophenone, 4-methylbenzophenone, 5-bromo-2-cyanopyridine or bromobenzene;
according to an embodiment of the invention, the alcohol may be a primary or secondary alcohol, such as methanol, ethanol, trifluoroethanol, benzyl alcohol, isopropanol.
According to an embodiment of the present invention, the catalytic halogenated hydrocarbon and alcohol ether or phenol production reaction comprises the following steps:
adding a photocatalyst, an auxiliary ligand, a halogenated aromatic compound, organic base, alcohol or water and an organic solvent into a photoreactor, irradiating by more than 400nm, and purifying after reaction to obtain a product.
According to an embodiment of the present invention, the photoreactor is preferably a light-transmitting reactor, such as a Pyrex glass reactor; further preferably, the photocatalytic reactor is sealed to remove oxygen.
According to an embodiment of the present invention, the concentration of the photocatalyst in the reaction system is 0.5 to 10g/L, preferably 2 g/L;
according to an embodiment of the present invention, the concentration of the ancillary ligand in the reaction system is 0.0003 to 0.02mol/L, preferably 0.004 mol/L;
according to an embodiment of the present invention, the concentration of the halogenated aromatic compound in the reaction system is 0.002 to 0.06mol/L, preferably 0.02 mol/L;
according to an embodiment of the invention, the molar ratio of the halogenated aromatic compound to the alcohol is from 1:20 to 100, such as from 1:40 to 80, exemplary from 1: 60;
according to embodiments of the present invention, the molar ratio of the halogenated aromatic compound to the organic base may be from 1:0.5 to 5, such as from 1:1 to 3, illustratively 1: 1.8;
according to an embodiment of the present invention, the organic solvent may be selected from at least one of dimethylformamide, dimethylacetamide, N-dimethylformamide dimethyl acetal, or dimethylsulfoxide;
according to embodiments of the invention, the reaction temperature may be 10-40 ℃, e.g. 25 ℃; the irradiation time may be 6h or more, examples 6h, 8h, 12 h; preferably, the irradiation is carried out under stirring.
Advantageous effects
The invention designs a single atom metal photocatalysis material and a catalyst composition prepared from the same by utilizing coordination of a carbon nitride-rich coordination nitrogen site and a metal, wherein a substrate and the metal are connected through a chemical bond in the catalyst, so that the electron transfer and the catalyst activation between the substrate and the metal are promoted; and further combining with a small molecule auxiliary ligand to construct an active metal center for carbon-oxygen cross coupling of a halogenated aromatic compound driven by visible light and alcohol/water to obtain ether or phenol and a recovered photocatalyst. The coupling of electron-deficient halogenated aromatic compound and alcohol/water is realized under mild conditions with high conversion number, the metal consumption is reduced on the premise of ensuring high selectivity of coupling products, the atomic efficiency is improved, the deposition inactivation is avoided, and the recycling of the catalyst is realized.
Drawings
Fig. 1 is a Ni element distribution of the catalyst prepared in example 1.
FIG. 2 is X-ray photoelectron spectroscopy (XPS) spectra of N1s (left) and Ni 2p (right) of the catalyst prepared in example 1.
FIG. 3 shows the catalyst prepared in example 1 and C3N4The emission spectrum of (2).
FIG. 4 is the gas spectrum of the product of the coupling reaction of p-bromoacetophenone and methanol in example 2.
FIG. 5 is a nuclear magnetic diagram of the product of the methanol coupling reaction of p-bromoacetophenone in example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
10g of urea was heated to 500 ℃ at a heating rate of 2 ℃/min and kept at 500 ℃ in air for 2 hours. The yellow solid product obtained was triturated and washed with water and ethanol. The sample was dried under vacuum for 12h to give C3N4. By mixing 1mmol/L of nickel chloride hexahydrate and C3N4(2g/L) was dispersed in a suspension of 50mL DMAc, and reacted for 6 hours. It was then centrifuged and the solid product washed twice and then dried in vacuo for 12 h. To obtain C3N4Carrying mononuclear nickel.
Example 2
Mixing 10mg of C3N4Ni, 0.02mmol of auxiliary ligand imidazole, 0.18mmol of organic base, 0.1mmol of p-bromoacetophenone and 6mmol of methanol are added into (DMAc), and the total volume of the reaction solution is 5 mL. The reaction mixture was then purged with argon under magnetic stirring for at least 15 minutes to remove oxygen. The photoreaction was performed under irradiation of a xenon lamp equipped with a 400nm stop filter. The reaction temperature was maintained at 25 ℃ by cooling with circulating water. After 8h of irradiation, the product p-methoxyacetophenone was obtained in 97% yield.
Comparative example 1
Mixing 10mg of C3N4Ni with 0.02mmol of the ancillary ligand imidazole, 0.18mmol of organic base, 0.1mmol of p-bromoacetophenone and 6mmol of methanol were added to 5mL of DMAc. The reaction mixture was then purged with argon under magnetic stirring for at least 15 minutes to remove oxygen. The reaction temperature was maintained at 25 ℃ by cooling with circulating water. After 8h of non-light reaction, no reactant conversion and no p-methoxyacetophenone are generated.
Comparative example 2
Mixing 10mg of C3N4Ni, 0.18mmol of organic base, 0.1mmol of p-bromoacetophenone and 6mmol of methanol were added to (DMAc) and the total volume of the reaction solution was 5 mL. The reaction mixture was then purged with argon under magnetic stirring for at least 15 minutes to remove oxygen. The photoreaction was performed under irradiation of a xenon lamp equipped with a 400nm stop filter. The reaction temperature was maintained at 25 ℃ by cooling with circulating water. After 8h of irradiation, the product p-methoxyacetophenone was obtained in 6% yield.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A monatomic metallic photocatalytic material in the form of a sheet having uniformly distributed metal atoms;
preferably, the metal is supported on the substrate surface in ionic form, with a metal loading of 0.04 to 0.36 wt%, for example 0.1 to 0.2 wt%.
2. The method for preparing the monatomic metallic photocatalytic material of claim 1, comprising the steps of:
step (1): heating and calcining the small-molecule precursor by a program to obtain a graphite type carbon nitride substrate;
step (2): and (2) dispersing the substrate in the step (1) in a polar organic solution of metal salt, and reacting to obtain the monatomic metal photocatalytic material.
3. The method according to claim 2, wherein the small molecule precursor in step (1) is at least one selected from urea, cyanamide, dicyandiamide, and melamine;
preferably, in step (1), the calcination is carried out in a muffle furnace; the calcination time is 1-5h, and the heating rate is 1-5 ℃/min;
preferably, step (1) further comprises the steps of washing and drying the substrate after the calcination; the cleaning step is that ethanol and water are used for cleaning for a plurality of times in sequence; the drying time may be 2-24 h.
4. The method according to claim 2 or 2, wherein in the step (2), the metal salt may be a nickel salt, such as nickel chloride, nickel nitrate, nickel sulfate, nickel phthalocyanine tetrasulfonic acid tetrasodium salt, or a hydrate thereof;
preferably, in the step (2), the polar organic solvent may be selected from at least one of dimethylformamide, dimethylacetamide, N-dimethylformamide dimethyl acetal, or dimethylsulfoxide;
preferably, in step (2), the mass ratio of the metal salt to the substrate is (1-60):500, for example (20-60): 500.
Preferably, in step (2), the concentration of the metal salt in the polar organic solvent may be 0.02 to 5mmol/L, for example, 0.05 to 2 mmol/L;
preferably, in the step (2), the concentration of the substrate in the polar organic solvent is 1-5 g/L;
preferably, in the step (2), the reaction time can be 1-12 h;
preferably, the step (2) further comprises washing at least twice with the reaction solvent after the reaction; and (4) cleaning and drying for 2-24 h.
5. Use of the monatomic metallic photocatalytic material according to claim 1 as a photocatalyst.
6. A photocatalyst comprising the monatomic metallic photocatalytic material according to claim 1.
7. A catalyst composition comprising the photocatalyst of claim 1 and an ancillary ligand.
Preferably, the ancillary ligand is an azaaryl compound, for example at least one selected from pyridine, imidazole, aminoimidazole, bipyridine, pyrrole, pyrazole and pyrimidine;
8. use of the photocatalyst according to claim 1 and/or the catalyst composition according to claim 7 in carbon-oxygen cross-coupling reactions, for example in catalysis of reactions of halogenated hydrocarbons and alcohols to produce ethers or phenols.
9. Use according to claim 1, characterized in that the halogenated hydrocarbon is a halogenated aromatic compound, such as p-bromoacetophenone, p-bromotrifluorotoluene, p-bromobenzonitrile, p-bromobenzaldehyde, ethyl p-bromobenzoate, m-bromoacetophenone, 4-methylbenzophenone, 5-bromo-2-cyanopyridine or bromobenzene;
preferably, the alcohol is a primary or secondary alcohol, such as methanol, ethanol, trifluoroethanol, benzyl alcohol, isopropanol.
10. Use according to claim 8 or 9, characterized in that said catalytic reaction of halogenated hydrocarbons with alcohols to produce ethers or phenols comprises the following steps:
adding a photocatalyst, an auxiliary ligand, a halogenated aromatic compound, organic base, alcohol or water and an organic solvent into a photoreactor, irradiating by more than 400nm, and purifying after reaction to obtain a product;
preferably, the concentration of the photocatalyst in the reaction system is 0.5-10 g/L;
preferably, the concentration of the auxiliary ligand in the reaction system is 0.0003-0.02 mol/L;
preferably, the concentration of the halogenated aromatic compound in the reaction system is 0.002-0.06 mol/L;
preferably, the molar ratio of the halogenated aromatic compound to the alcohol is from 1:20 to 100;
preferably, the molar ratio of the halogenated aromatic compound to the organic base may be 1:0.5 to 5.
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| CN115090327A (en) * | 2022-06-10 | 2022-09-23 | 中国科学院化学研究所 | Covalent organic framework photocatalytic material with controllable coordination site number and loaded metal monoatomic atom, and preparation method and application thereof |
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| CN113058653A (en) * | 2021-03-26 | 2021-07-02 | 兰州大学 | Catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile and preparation method thereof |
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| CN115090327A (en) * | 2022-06-10 | 2022-09-23 | 中国科学院化学研究所 | Covalent organic framework photocatalytic material with controllable coordination site number and loaded metal monoatomic atom, and preparation method and application thereof |
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