CN112920055A - Visible light catalytic one-pot hydrogenation and amidation method for nitroarene and carboxylic acid - Google Patents
Visible light catalytic one-pot hydrogenation and amidation method for nitroarene and carboxylic acid Download PDFInfo
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- CN112920055A CN112920055A CN202110135438.0A CN202110135438A CN112920055A CN 112920055 A CN112920055 A CN 112920055A CN 202110135438 A CN202110135438 A CN 202110135438A CN 112920055 A CN112920055 A CN 112920055A
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- 238000007112 amidation reaction Methods 0.000 title claims abstract description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- 230000009435 amidation Effects 0.000 title claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 64
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- -1 aromatic nitro compounds Chemical class 0.000 claims abstract description 9
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 238000010523 cascade reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 62
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 150000002828 nitro derivatives Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 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
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 abstract 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000010936 titanium Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 11
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ARKIFHPFTHVKDT-UHFFFAOYSA-N 1-(3-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC([N+]([O-])=O)=C1 ARKIFHPFTHVKDT-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 description 2
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical class C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location 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
- 239000002159 nanocrystal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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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
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- 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
Abstract
The invention discloses a method for one-pot hydrogenation and amidation reaction of visible light catalytic nitroaromatic and carboxylic acid, which is characterized in that uniformly dispersed Pt nano particles on an N-doped titanium dioxide/titanium carbide (MXene) heterojunction are prepared as a photocatalyst (3% Pt/N-TiO)2/Ti3C2) And the catalysts are used for the aromatic nitro compounds andthe amide product is prepared by the tandem reaction of carboxylic acids. 3% Pt/N-TiO2/Ti3C2Has excellent serial hydrogenation, amidation activity and chemical selectivity of aromatic nitro compound and carboxylic acid under the irradiation of visible light. 3% Pt/N-TiO2/Ti3C2The excellent catalytic performance is attributed to TiO2And conductive Ti3C2The efficiency of separating the photo-generated electrons from the holes is improved through short-range directional transmission of charges. The preparation method of the catalyst is simple and easy to operate, can be used for photocatalytic high-efficiency one-pot hydrogenation and amidation reactions, and has mild reaction conditions and easy recycling of the catalyst.
Description
Technical Field
The invention relates to a method for one-pot hydrogenation and amidation reaction of nitryl aromatic hydrocarbon and carboxylic acid by visible light catalysis.
Background
Amides are a very common functional group in natural products or modern organic synthesis and are widely used by medicinal chemists. Conventional amide synthesis methods include Dicyclohexylcarbodiimide (DCC)/N, N' -carbonyldiimidazole activation, or the reaction of amines with acid halides, anhydrides, esters, acyl azides, and the like. It is well known that the most preferred method of amide synthesis is the direct condensation of an amine with a carboxylic acid. However, the direct condensation process requires a fairly high temperature due to the non-reactive ammonium carboxylate intermediate. Thus, avoiding low atom economy amide synthesis is considered to be a primary challenge in organic chemistry.
The pursuit of new environmentally friendly reaction processes with high efficiency and minimal waste generation has become one of the most important goals in the chemical field. One-pot series/cascade reactions generally require the multifunctional catalyst to have different catalytically active sites in a positionally isolated manner to maintain independent functions. The occurrence of multiple step reactions in one reactor without the need for isolation of intermediates is of great advantage and has attracted extensive research interest. In a one-pot series/cascade reaction, it is quite attractive to drive the synthesis process with light. MXenes is a raised two-dimensional transition metal carbide and/or carbonitride of the general formula Mn+1XnTx（n=1，2，3；TxGroup = OH, O, F). MXene has excellent electron conductivity, so that charges are more easily transferred from a semiconductor to MXene, and the separation efficiency of electrons and holes is improved. MXene is considered one of the most promising photocatalytic materials because of its unique properties as described above.
Disclosure of Invention
The invention is realized by adding Ti3C2In-situ growth of TiO on nano-scale2Then doping TiO with melamine or urea2Formation of N-TiO2/Ti3C2(ii) a Subsequently on N-TiO2/Ti3C2The Pt nano particles with smaller diameter are well loaded to form 3 percent of Pt/N-TiO2/Ti3C2A catalytic material. 3% Pt/N-TiO2/Ti3C2The catalyst shows good one-pot hydrogenation and amidation activity and chemoselectivity of the nitroarene and the carboxylic acid under the irradiation of visible light. 3% Pt/N-TiO2/Ti3C2The good catalytic performance is due to TiO2And conductive Ti3C2The efficiency of separating the photo-generated electrons from the holes is improved through short-range directional transmission of charges.
The invention provides a one-pot hydrogenation and amidation reaction method for visible light catalysis of nitroarene and carboxylic acid.
The adopted technical scheme is as follows: by reaction at Ti3C2In-situ growth of TiO on nano-scale2Then on TiO2The nano-chip is N-doped by adopting melamine or urea, and then Pt nano-particles with the average diameter of 3.3nm are loaded to prepare 3 percent Pt/N-TiO2/Ti3C2A heterojunction; the photocatalytic high-efficiency one-pot hydrogenation and amidation reaction is characterized in that: 3% Pt/N-TiO2/Ti3C2Has excellent serial hydrogenation, amidation activity and chemical selectivity of aromatic nitro compound and carboxylic acid under the irradiation of visible light. 3% Pt/N-TiO2/Ti3C2The excellent catalytic performance is due to TiO2And conductive Ti3C2The efficiency of separating the photo-generated electrons from the holes is improved through short-range directional transmission of charges. The preparation method of the catalyst is simple and easy to operate, can be used for one-pot hydrogenation and amidation of the photocatalytic high-efficiency nitroarene and the carboxylic acid, and has mild reaction conditions and easy recycling of the catalyst.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: the catalyst has no catalytic activity in the absence of illumination and has higher catalytic activity under the acceleration of light.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: the adopted illumination color can be one or a mixture of a plurality of red, orange, yellow, green, blue, indigo and purple, the hydrogen pressure in the one-pot hydrogenation process is 0.1-100 atmospheric pressures, and the catalyst is easy to recycle.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: the load metal can be one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, gold and silver, and the adopted N source is melamine or urea.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: the substrate for tandem hydrogenation and amidation tandem reaction with carboxylic acid can be nitro compound, nitrile compound, etc.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: the acid substrate for serial hydrogenation and amidation may be fatty acid, aromatic acid, etc.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: the alkaline additive promotes the performance of one-pot hydrogenation and amidation reactions, and the efficiency of the one-pot hydrogenation and amidation reactions is reduced in the presence of the alkaline additive.
The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroaromatic and carboxylic acid is characterized in that: 3% Pt/N-TiO2/Ti3C2The excellent catalytic performance is due to TiO2And conductive Ti3C2The efficiency of separating the photo-generated electrons from the holes is improved through short-range directional transmission of charges.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the photocatalyst comprises the following steps: TiO 22/Ti3C2Is to mix Ti at 160 DEG C3C2Hydrothermal oxidation for 12 hours. TiO 22@ C preparation: mixing Ti3C2Placing in a crucible at 550 deg.C for 5 min-1The temperature rising rate of (2) was calcined in air for 2 hours. N is a radical of-TiO2/Ti3C2And N-TiO2@ C preparation procedure: 200 mg TiO2/Ti3C2Or TiO2@ C, 100mg of melamine or 144mg of urea (the nitrogen content is the same as that of melamine) are added to 15ml of distilled water and mixed uniformly. Drying the mixture and heating at 400 deg.C for 5 deg.C min-1Heating rate is in N2And calcining for 2 hours. 3% Pt/N-TiO2/Ti3C2And 3% Pt/N-TiO2Preparation of @ C: 2 mL of KOH solution (0.2 mmol), 0.1mmol H2PtCl6.6H2O，0.63g N-TiO2/Ti3C2Or N-TiO2@ C was added to 18 mL of deionized water and stirred to complete the full load. 0.36mmol of NaBH was introduced with continuous vigorous stirring4An aqueous solution. The solid was separated by repeated centrifugation and washed with water and ethanol. The resulting solid was then dried under vacuum.
A visible light catalyzed one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid mainly comprises the following steps: visible light induced one-pot hydrogenation and amidation reaction are carried out under a reaction tube and a commercial LED lamp. Typically, 1mmol of nitro compound is introduced into a mixture of 10mg of catalyst and 3 ml of acid solution (or a mixture of acid and organic solvent). Before the reaction, the reaction solution is treated with 1 atm N2Or H2And (4) saturation. The product was separated by flash chromatography or high speed centrifugation, analyzed by GC-MS using an HP-5 capillary column, and compared to known compounds.
Drawings
FIG. 1 shows the preparation of catalyst a) Ti in example 13C2;b) N-TiO2/Ti3C2; c) 3%Pt/N-TiO2/Ti3C2SEM image of (d).
FIG. 2 is a graph showing the preparation of catalyst 3% Pt/N-TiO according to example 12/Ti3C2TEM image a), HRTEM image b) and TEM image d) after successive cycles.
FIG. 3 is a graph showing the preparation of catalyst 3% Pt/N-TiO according to example 12/Ti3C2XPS spectra of (a): a) full spectrum, b) Pt 4f, C) Ti2p, d) O1s e) C1 s and f) N1 s.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1:
TiO2/Ti3C2is to mix Ti at 160 DEG C3C2Hydrothermal oxidation for 12 hours. TiO 22@ C preparation: mixing Ti3C2Placing in a crucible at 550 deg.C for 5 min-1The temperature rising rate of (2) was calcined in air for 2 hours. N-TiO 22/Ti3C2And N-TiO2@ C preparation procedure: 200 mg TiO2/Ti3C2Or TiO2@ C, 100mg of melamine or 144mg of urea (the nitrogen content is the same as that of melamine) are added to 15ml of distilled water and mixed uniformly. Drying the mixture and heating at 400 deg.C for 5 deg.C min-1Heating rate is in N2And calcining for 2 hours.
3%Pt/N-TiO2/Ti3C2And 3% Pt/N-TiO2Preparation of @ C: 2 mL of KOH solution (0.2 mmol), 0.1mmol H2PtCl6.6H2O，0.63g N-TiO2/Ti3C2Or N-TiO2@ C was added to 18 mL of deionized water and stirred to complete the full load. 0.36mmol of NaBH was introduced with continuous vigorous stirring4An aqueous solution. The solid was separated by repeated centrifugation and washed with water and ethanol. The resulting solid was then dried under vacuum.
A visible light catalyzed one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid mainly comprises the following steps: visible light induced one-pot hydrogenation and amidation reaction are carried out under a reaction tube and a commercial LED lamp. Typically, 1mmol of nitro compound is introduced into a mixture of 10mg of catalyst and 3 ml of acid solution (or a mixture of acid and organic solvent). Before the reaction, the reaction solution is treated with 1 atm N2Or H2And (4) saturation. The product was separated by flash chromatography or high speed centrifugation, analyzed by GC-MS using an HP-5 capillary column, and compared to known compounds.
FIG. 1 shows the preparation of catalyst a) Ti in example 13C2;b) N-TiO2/Ti3C2; c) 3%Pt/N-TiO2/Ti3C2SEM image of (d). FIG. 1a shows a stack of layers Ti3C2Scanning Electron Microscope (SEM) images of (a). FIG. 2b is a melamine N doped TiO2/Ti3C2（N-TiO2/Ti3C2) SEM image of (1), characterized in that in Ti3C2Uniformly growing N-doped TiO on the surface and the intermediate layer of the MXene layer2. With Ti3C2In contrast, N-TiO2/Ti3C2Becomes rougher and the deposited layer becomes thicker, which indicates that Ti is present3C2Is coated with N-TiO2Effectively wrapping. After platinum loading and reduction to Nanoparticles (NPs) (fig. 1 c), due to Ti3C2Support Retention, 3% Pt/N-TiO2/Ti3C2Is almost maintained at N-TiO2/Ti3C2The features observed in (a). On the other hand, in the absence of Ti3C2In the presence of 3% Pt/N-TiO2No significant buildup was observed at @ C.
FIG. 2 is a graph showing the preparation of catalyst 3% Pt/N-TiO according to example 12/Ti3C2TEM image a), HRTEM image b) and TEM image d) after successive cycles. For N-TiO with Transmission Electron Microscope (TEM)2/Ti3C2Detailed information of the upper metallic Pt nanoparticles was characterized. 3% Pt/N-TiO2/Ti3C2The TEM image of (FIG. 2 a) clearly shows that Pt nanoparticles with an average diameter of 3.3nm are uniformly distributed in N-TiO2/Ti3C2The above. Although TiO is grown in situ2N-TiO after N-doping and PtNPs loading2And Pt NPs are covered with Ti3C2But Pt NPs (0.23 nm), N-TiO are simultaneously observed in a high-resolution transmission electron micrograph2(0.27 nm) and Ti3C2(0.35 nm) lattice fringes (FIG. 2 b), ensuring Pt NPs, N-TiO2Nanocrystal and Ti3C2Can be fully contacted with reactants and play the role of an active center in a photocatalytic reaction。
FIG. 3 is a graph showing the preparation of catalyst 3% Pt/N-TiO according to example 12/Ti3C2XPS spectra of (a): a) full spectrum, b) Pt 4f, C) Ti2p, d) O1s e) C1 s and f) N1 s. 3% Pt/N-TiO was analyzed by XPS2/Ti3C2The nature of (c). XPS characterization indicated the presence of platinum, titanium, oxygen, carbon and nitrogen (fig. 3 a), which means successful preparation of the heterojunction. Pt 4f is resolved into two components, and the binding energy of 70.9 and 74.3 eV is the peaks of 4f7/2 and 4f5/2 of metal Pt; 72.6 and 75.8 eV are the 4f7/2 and 4f5/2 peaks of Pt (II) (FIG. 3 b). This indicates that metallic platinum is the major species with a small amount of platinum (II) present. 3% Pt/N-TiO2/Ti3C2The spectrum of the catalyst in the Ti2p region is shown in figure 3 c. With TiO2By comparison, 3% Pt/N-TiO2/Ti3C2The Ti2p (458.8 and 464.3 eV) in (b) is shifted negatively. The negative shift of the peak to lower binding energy may be due to the formation of an O-Ti-N band in the lattice as a result of doping. XPS spectra (FIG. 3 d) of O1s can be resolved into two oxygen components of 530.1 eV (Ti-O-Ti) and 531.7 eV (Ti-OH). C1 s in fig. 3e can be fitted to three peaks: 284.7 eV (C-C bond); 286.4 eV, ascribed to a C-O bond; and 288.2 eV, assigned to Ti-O-C, due to the substitution of carbon atoms into the titanium lattice. The XPS spectrum for N1 s in FIG. 3f has two peaks at 399.2 and 404.5 eV. 399.2 eV is due to the presence of lattice oxygen substituted by N atoms (O-Ti-N).
Example 2 (table 1, entry 2):
in a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst and 1mmol nitrobenzene, before reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of nitrobenzene is 100.0 percent, and the selectivity of amidation products is 64.0 percent.
Example 3: (Table 1, entry 3)
In self-made reactors with cooling systemsIn a reaction tube, 10mg of 3% Pt/N-TiO was added to 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol nitrobenzene, before reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of nitrobenzene is 100.0 percent, and the selectivity of amidation products is 100.0 percent. No significant decrease in photocatalytic activity and chemical selectivity was observed for the catalyst after 5 cycles of centrifugation. In addition, no loss of Pt during cycling was detected by ICP-OES.
Example 4: (Table 1, entry 9)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2@ C catalyst, K3PO4(1 mmol) and 1mmol nitrobenzene, before reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction was carried out for 24 hours under the irradiation of a blue LED lamp, the nitrobenzene conversion was 67.6%, and the amidation product selectivity was 86.7%.
Example 5: (Table 2, entry 3)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO was added to 3 ml of propionic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol nitrobenzene, before reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of nitrobenzene is 99.8 percent, and the selectivity of amidation products is 91.9 percent.
Example 6: (Table 2, entry 6)
In a self-made reaction tube with a cooling system, 10mg of 3 percent Pt/N-TiO is added into 3 ml of isobutyric acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol nitrobenzene, before reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 Reacting for 24 hours under the irradiation of a blue LED lamp, wherein the conversion rate of nitrobenzene is 100.0 percent, and amidatingThe product selectivity was 90.8%.
Example 7: (Table 3, entry 4)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol of p-nitrotoluene, and before the reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of the p-nitrotoluene is 100.0 percent, and the selectivity of amidation products is 100.0 percent.
Example 8: (Table 3, entry 6)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol of p-methoxynitrobenzene, before the reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of the p-methoxynitrobenzene is 100.0 percent, and the selectivity of amidation products is 85.3 percent.
Example 9: (Table 3, entry 8)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol of p-chloronitrobenzene, before the reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of the p-chloronitrobenzene is 100.0 percent, and the selectivity of amidation products is 94.3 percent.
Example 10: (Table 3, entry 10)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol of m-nitroacetophenone, and reacting the reaction solution with 1 atm of H2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of the m-nitroacetophenone is 100.0 percent, and the selectivity of the amidation product is 89.5 percent.
Example 11: (Table 4, entry 4)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol), 1mmol nitrobenzene and 100. mu.M KBrO3As an electron scavenger, 1 atm H is used for the reaction solution before the reaction2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of nitrobenzene is 27.0 percent, and the selectivity of amidation products is 89.5 percent. When the e-scavenger KBrO3When a catalytic system is introduced, the photocatalytic activity is obviously reduced, which indicates that the reduction of nitrobenzene is accelerated by photo-generated electrons.
Example 12: table 4, entry 5)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol), 1mmol nitrobenzene and 100. mu.M TEOA as hole scavengers, 1 atm H for the reaction mixture before reaction2And (4) saturation. Commercial 0.75 Wcm-2 The reaction is carried out for 24 hours under the irradiation of a blue LED lamp, the conversion rate of nitrobenzene is 90.0 percent, and the selectivity of amidation products is 80.8 percent. When the h + scavenger TEOA is introduced into the catalytic system, the chemoselectivity of the amidation product is reduced, and therefore the photogenerated holes contribute to some extent to the amidation step.
Example 13: table 4, entry 7)
In a self-made reaction tube with a cooling system, 10mg of 3% Pt/N-TiO is added into 3 ml of acetic acid solution benzene2/Ti3C catalyst, K3PO4(1 mmol) and 1mmol nitrobenzene, before reaction, the reaction solution is treated with 1 atm H2And (4) saturation. Without illumination 60oAnd C, reacting for 24 hours, wherein the conversion rate of nitrobenzene is 5.7 percent, and the selectivity of amidation products is 0.0 percent.
Claims (8)
1. A method for visible light catalysis of one-pot hydrogenation and amidation reaction of nitroaromatic and carboxylic acid is characterized in that the catalytic material is prepared by the following steps: by reaction at Ti3C2In-situ growth of TiO on nano-scale2Then on TiO2The preparation method adopts melamine or urea to carry out N doping, and then Pt nano particles with the average diameter of 3.3nm are loaded to prepare 3 percent Pt/N-TiO2/Ti3C2A heterojunction; the photocatalytic high-efficiency one-pot hydrogenation and amidation reaction is characterized in that: 3% Pt/N-TiO2/Ti3C2Has excellent serial hydrogenation, amidation activity and chemical selectivity of aromatic nitro compound and carboxylic acid under the irradiation of visible light, and 3 percent of Pt/N-TiO2/Ti3C2The excellent catalytic performance is due to TiO2And conductive Ti3C2The efficiency of separating the photo-generated electrons from the holes is improved through short-range directional transmission of charges.
2. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: the catalyst has no catalytic activity in the absence of illumination and has higher catalytic activity under the acceleration of light.
3. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: the adopted illumination color can be one or a mixture of a plurality of red, orange, yellow, green, blue, indigo and purple, the hydrogen pressure in the one-pot hydrogenation process is 0.1-100 atmospheric pressures, and the catalyst is easy to recycle.
4. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: the load metal can be one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, gold and silver, and the adopted N source is melamine or urea.
5. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: the substrate for tandem hydrogenation and amidation tandem reaction with carboxylic acid can be nitro compound, nitrile compound, etc.
6. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: the acid substrate for serial hydrogenation and amidation may be fatty acid, aromatic acid, etc.
7. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: the alkaline additive promotes the performance of one-pot hydrogenation and amidation reactions, and the efficiency of one-pot hydrogenation and amidation reactions is reduced in the absence of the alkaline additive.
8. The visible light catalytic one-pot hydrogenation and amidation reaction method of nitroarene and carboxylic acid as claimed in claim 1, wherein the method comprises the following steps: 3% Pt/N-TiO2/Ti3C2The excellent catalytic performance is due to TiO2And conductive Ti3C2The efficiency of separating the photo-generated electrons from the holes is improved through short-range directional transmission of charges.
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