CN111992206A - Ultra-dispersed noble metal heterogeneous catalyst and application thereof - Google Patents
Ultra-dispersed noble metal heterogeneous catalyst and application thereof Download PDFInfo
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 59
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 70
- 239000002923 metal particle Substances 0.000 claims abstract description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 239000008247 solid mixture Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910010251 TiO2(B) Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 239000012694 precious metal precursor Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 61
- 239000000463 material Substances 0.000 description 40
- 229910001220 stainless steel Inorganic materials 0.000 description 32
- 239000010935 stainless steel Substances 0.000 description 32
- 229910003081 TiO2−x Inorganic materials 0.000 description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 30
- GKJSZXGYFJBYRQ-UHFFFAOYSA-N 6-chloroquinoline Chemical compound N1=CC=CC2=CC(Cl)=CC=C21 GKJSZXGYFJBYRQ-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000012295 chemical reaction liquid Substances 0.000 description 21
- 239000002105 nanoparticle Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 13
- 230000003993 interaction Effects 0.000 description 13
- PASUADIMFGAUDB-UHFFFAOYSA-N 6-chloro-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(Cl)=CC=C21 PASUADIMFGAUDB-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- RDRJDYMTRYTFSR-UHFFFAOYSA-N 1-chloro-3,4-dihydro-2h-quinoline Chemical compound C1=CC=C2N(Cl)CCCC2=C1 RDRJDYMTRYTFSR-UHFFFAOYSA-N 0.000 description 5
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003248 quinolines Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 Platinum Group Metals Chemical class 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YGIXHMZHQGPWDE-UHFFFAOYSA-N 6,6-dichloro-5H-quinoline Chemical compound ClC1(CC=2C=CC=NC=2C=C1)Cl YGIXHMZHQGPWDE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/18—Halogen atoms or nitro radicals
Abstract
The invention discloses a super-dispersed noble metal heterogeneous catalyst and application thereof, wherein the catalyst comprises a titanium dioxide carrier with oxygen vacancies and noble metal particles loaded on the titanium dioxide carrier, the load capacity of the noble metal particles is 10-25%, the noble metal particles are Au, Ag, Rh, Os, Ir, Ru, Pt or Pd particles, and preferably Ru or Pd particles; the average particle diameter of the noble metal particles is 1 to 3 nm. Compared with the common titanium dioxide supported noble metal catalyst, the heterogeneous catalyst has the advantages that noble metal particles are uniformly dispersed, and the particle size of the noble metal particles is not agglomerated along with the increase of the supported amount.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a super-dispersed noble metal heterogeneous catalyst and application thereof.
Background
Supported metal catalysts are one of the most common heterogeneous catalysts and are widely used in the chemical industry. Both the metal and the support are very important because in many cases the support not only stabilizes the dispersed metal but also changes its morphology and electronic structure through the interaction of the metal support, changing the performance of the catalyst. In particular, Strong Metal Support Interaction (SMSI), a term of invention by Tauster et al (Garten, J. Am. chem. Soc. 1978,100, 170-175), has been studied for a long time to describe the loss of the ability of Platinum Group Metals (PGMs) supported on reducible oxides to adsorb small molecules after high temperature reduction. SMSI enables charge transfer and mass transfer from the carrier to the metal; thereby greatly improving the stability of the catalyst and improving the catalytic performance of the catalyst.
Noble metal nanoparticles are of great interest for their wide application in a variety of catalysts. The catalytic properties of nanoparticles are highly sensitive to size, size distribution and metal support interactions. In general, the reduction in size of metal nanoparticles provides a great opportunity to achieve high surface to volume ratios, thereby increasing the efficiency of catalytic applications. Efforts have been made to develop synthetic routes to obtain noble metal nanoparticles smaller than 5nm, which typically involve the use of organic capping molecules or polymeric stabilizers. For example: ruthenium (Ru) plays an important role in many catalytic reactions, including hydrogenation, CO oxidation and fischer-tropsch synthesis reactions. Although ruthenium nanoparticles of different sizes were synthesized using different capping agents, few reports have been made on the synthesis of ruthenium nanoparticles in a sub-2 nm system.
Disclosure of Invention
In view of the above-mentioned problems of the prior art, it is an object of the present invention to provide a heterogeneous catalyst of noble metal which is ultra-dispersed on a catalyst support and is stable to air, water and heat, and which is synthesized by a specific method and contains noble metal particles, and which does not exhibit a phenomenon of agglomeration in a large area with an increase in the amount of metal supported.
The super-dispersed noble metal heterogeneous catalyst is characterized by comprising a titanium dioxide carrier with oxygen vacancies and noble metal particles loaded on the titanium dioxide carrier, wherein the loading amount of the noble metal particles is 10-25%, and the noble metal particles are Au, Ag, Rh, Os, Ir, Ru, Pt or Pd particles, preferably Ru or Pd particles; the average particle diameter of the noble metal particles is 1 to 3 nm.
The super-dispersed noble metal heterogeneous catalyst is characterized in that the preparation method of the titanium dioxide with oxygen vacancy comprises the following steps: with TiO2(B) Calcining the raw materials in an inert gas atmosphere at the temperature of 500-1200 ℃ for 0.5-8 h to obtain the titanium dioxide with the oxygen vacancy.
The super-dispersed noble metal heterogeneous catalyst is characterized in that the inert gas is nitrogen.
The heterogeneous catalyst of the ultra-dispersed noble metal is characterized in that the preparation method of the heterogeneous catalyst comprises the following steps:
1) adding the titanium dioxide with the oxygen vacancy into an aqueous solution of a noble metal precursor, stirring and mixing uniformly to enable the noble metal precursor to be adsorbed on the titanium dioxide, and then heating and stirring at 60-80 ℃ until the moisture is completely volatilized to obtain a solid mixture;
2) placing the solid mixture obtained in the step 1) in a tubular furnace, and roasting in an atmosphere of introducing hydrogen to reduce the precious metal precursor loaded on the titanium dioxide into precious metal particles, thus obtaining the heterogeneous catalyst; wherein the noble metal precursor is chloride or nitrate of Au, Ag, Rh, Os, Ir, Ru, Pt or Pd metal, preferably chloride of Ru or Pd metal;
in the step 2), the roasting temperature is 200-600 ℃, preferably 250-500 ℃.
The application of the noble metal heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the quinoline compounds are mixed with a solvent, and the mixed reaction liquid and hydrogen carry out selective hydrogenation reaction under the action of the heterogeneous catalyst to generate hydrogenated quinoline compounds; wherein the reaction temperature is 20-100 ℃, and the reaction pressure is 0.5-2 MPa; the solvent is ethanol, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, N-dimethylformamide, N-hexane or toluene.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. in the preparation process of the catalyst carrier, TiO is selected as titanium dioxide2(B) And TiO 22(B) Has a flaky multi-layer structure which is unstable at high temperature and in which O is desorbed during high-temperature calcination in an inert atmosphere to form oxygen vacancies. In the catalyst prepared by the invention, due to the strong interaction between the noble metal particles and the titanium dioxide carrier with oxygen vacancies, the electron transfer between the noble metal and the carrier occurs, and the noble metal is rich in charges and is not easy to agglomerate, thereby realizing high dispersion.
2. In the heterogeneous catalyst, due to the strong interaction between the noble metal particles and the titanium dioxide carrier with oxygen vacancies and the effectiveness of hydrogen reduction (namely, the hydrogen can effectively reduce the ionic noble metal into simple substances), the noble metal particles of the heterogeneous catalyst prepared by the invention have uniform size and good dispersity, the size of the metal nanoparticles is not increased along with the increase of the loading amount, and the average diameter of the noble metal particles of the catalysts with different loading amounts is always 1-3 nm. The heterogeneous catalyst is stable to air, water and heat, the hydrogenation activity of the catalyst for catalyzing 6-chloroquinoline is not reduced after the catalyst exists in the air for 5 months, and the metal valence state is kept unchanged.
3. The invention utilizes Ru and TiO with oxygen vacancy2The Ru-based catalyst with ultra-dispersion is synthesized by a simple synthesis method, even under the condition of high loading of 20 percent, the Ru still has ultra-high dispersion and has good activity in the quinoline hydrogenation reaction.
Drawings
FIG. 1 is a HRTEM image of the catalyst obtained in example 1;
FIG. 2 is a HRTEM image of the catalyst obtained in example 2;
FIG. 3 is a HRTEM image of the catalyst obtained in example 3;
FIG. 4 is a HRTEM image of the catalyst obtained in example 5;
FIG. 5 is a HRTEM image of the catalyst obtained in example 6.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 based on TiO2-xHeterogeneous catalyst loaded with 10% Ru
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 4ml of previously prepared RuCl were added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Ru catalyst, with a Ru loading of 10%.
Example 2 based on TiO2-xHeterogeneous catalyst loaded with 12% Ru
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 4.8ml of previously prepared RuCl were added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
The solid mixture obtained above was placed in a tube furnaceCalcining at 300 ℃ for 1h in hydrogen atmosphere to obtain TiO2-xThe supported Ru catalyst had a Ru loading of 12%.
Example 3 TiO-based2-xHeterogeneous catalyst loaded with 15% Ru
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 6ml of previously prepared RuCl were added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Ru catalyst with a Ru loading of 15%.
Example 4 based on TiO2-xHeterogeneous catalyst loaded with 20% Ru
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, plus 8ml of previously prepared RuCl3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xSupported Ru catalystsCatalyst, Ru loading was 20%.
Example 5 based on TiO2-xHeterogeneous catalyst loaded with 25% Ru
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 10ml of previously prepared RuCl were added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Ru catalyst with a Ru loading of 25%.
Example 6 based on TiO2-xHeterogeneous catalyst loaded with 20% Pd
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 6.7ml of PdCl prepared beforehand are then added2Aqueous solution (PdCl)2The concentration of the aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that PdCl is added3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Pd after later-stage calcination are closely and uniformly combined.
The prepared solid mixture is placed in a tube furnace and calcined for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xSupported Pd catalyst, Pd loading 20%.
Example 7 example 1Medium TiO 22-xCharacterization of the 10% Ru Supported catalyst
The TiO obtained in example 1 was examined by high-resolution transmission electron microscope (HRTEM)2-xThe supported Ru catalyst was characterized, and the characterization results are shown in FIG. 1, which confirmed that the catalyst consisted of titanium dioxide and the nano-metal Ru. Ru nano particles are uniformly distributed on TiO2-xOn the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 1.8 nm by counting 150 nanometer Ru metal particles.
Example 8 TiO in example 22-xCharacterization of the 12% Ru-Supported catalyst
The TiO obtained in example 2 was examined by high-resolution transmission electron microscope (HRTEM)2-xThe supported Ru catalyst was characterized, and the characterization results are shown in FIG. 2, which confirmed that the catalyst consisted of titanium dioxide and the nano-metal Ru. Ru nano particles are uniformly distributed on TiO2-xOn the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 1.9nm by counting 150 nanometer Ru metal particles.
Example 9 TiO in example 32-xCharacterization of the 15% Ru-Supported catalyst
The TiO obtained in example 3 was examined by high-resolution transmission electron microscope (HRTEM)2-xThe supported Ru catalyst was characterized, and the characterization results are shown in FIG. 3, which confirmed that the catalyst consisted of titanium dioxide and the nano-metal Ru. Ru nano particles are uniformly distributed on TiO2-xOn the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 1.7nm by counting 150 nanometer Ru metal particles.
Example 10 example 4 TiO2-xCharacterization of the 20% Ru-Supported catalyst
The TiO obtained in example 4 was examined by high-resolution transmission electron microscope (HRTEM)2-xCharacterization of the supported Ru catalyst confirmed that the catalyst consisted of twoTitanium oxide and nano metal Ru. Ru nano particles are uniformly distributed on TiO2-xOn the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 2.4nm by counting 150 nanometer Ru metal particles.
Example 11 TiO in example 52-xCharacterization of 25% Ru-Supported catalyst
The TiO obtained in example 5 was examined by high-resolution transmission electron microscope (HRTEM)2-xThe supported Ru catalyst was characterized, and the characterization results are shown in FIG. 4, which confirmed that the catalyst consisted of titanium dioxide and the nano-metal Ru. Ru nano particles are uniformly distributed on TiO2-xOn the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 2.5nm by counting 150 nanometer Ru metal particles.
Example 13 TiO in example 62-xCharacterization of the 20% Pd Supported catalyst
The TiO obtained in example 6 was examined by high-resolution transmission electron microscope (HRTEM)2-xThe supported Pd catalyst was characterized, and the characterization results are shown in fig. 5, confirming that the catalyst was composed of titania together with nano-metallic Pd. Pd nano particles are uniformly distributed in TiO2-xOn the material, Pd and titanium dioxide are in close contact, which shows that the Pd and the titanium dioxide have obvious interaction. The average particle diameter of the Pd nano particles is 3.1nm by counting 150 nano Pd metal particles.
EXAMPLE 14 preparation of 6 chloro-tetrahydroquinoline by hydrogenation of 6 chloro-quinoline over the heterogeneous catalyst prepared in example 1
After 118. mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in example 1 and 10mL of methylene chloride were charged into a 50 mL stainless steel autoclave, the inside of the stainless steel autoclave was purged with hydrogen 3 times (i.e., the inside of the stainless steel autoclave was purged with air by replacing the inside with hydrogen, the inside of the stainless steel autoclave was purged with air, which is equivalent to the following example), charged with hydrogen to 1MPa and sealed, heated in a 40 ℃ water bath, magnetically stirred, and subjected to a selective hydrogenation reaction for 5.10 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating by detection that the conversion rate of the 6-chloroquinoline is 98% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 97%.
EXAMPLE 15 preparation of 6 chloro-tetrahydroquinoline by hydrogenation of 6 chloro-quinoline over the heterogeneous catalyst prepared in example 2
Mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in example 2 and 10mL of methylene chloride were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, hydrogen was charged to 1MPa and sealed, and the mixture was heated in a water bath at 40 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 4.50 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the 6-chloroquinoline is 99% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 90%.
EXAMPLE 16 preparation of 6 chloro-tetrahydro 6 chloro-quinoline by hydrogenation of 6 chloro-quinoline over the heterogeneous catalyst prepared in example 3
Mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in example 3 and 10mL of methylene chloride were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, charging hydrogen to 1MPa and sealing were carried out, and the mixture was heated in a water bath at 40 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 4.20 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating that the conversion rate of the obtained 6-chloroquinoline is 98% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 95%.
Example 17 preparation of 6 chloro-tetrahydroquinoline by hydrogenation of 6 chloro-quinoline over the heterogeneous catalyst prepared in example 4
Mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in example 4 and 10mL of methylene chloride were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, charging hydrogen to 1MPa and sealing were carried out, and the mixture was heated in a water bath at 40 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3.15 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the 6-chloroquinoline is 99% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 96%.
EXAMPLE 18 preparation of 6 chloro-tetrahydroquinoline by hydrogenation of 6 chloro-quinoline over the heterogeneous catalyst prepared in example 5
Mu.l of 6-chloroquinoline, 10 mg of the catalyst of example 5 and 10mL of dichloromethane were charged into a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, charging and sealing were performed, and heating in a water bath at 40 ℃ was performed with magnetic stirring to perform selective hydrogenation for 2.80 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the 6-chloroquinoline is 99% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 96%.
EXAMPLE 19 preparation of 6 chloro-tetrahydroquinoline by hydrogenation of 6 chloroquinoline over the heterogeneous catalyst prepared in example 6
Mu.l of 6-chloro-6-chloroquinoline, 10 mg of the catalyst of example 6 and 10mL of dichloromethane were charged into a 50 mL stainless steel autoclave, and after 3 times of charging and discharging of hydrogen gas in the stainless steel autoclave, charging of hydrogen gas was carried out to 1MPa and sealing, and the mixture was heated in a water bath at 25 ℃ with magnetic stirring to carry out selective hydrogenation reaction for 0.50 h. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the 6-chloroquinoline is 99% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 94%.
Examples 14-19 show that titania with vacancies supporting different loadings of noble metal all have good activity and selectivity for the hydrogenation of 6-chloroquinoline.
EXAMPLE 20 preparation of 6-chlorotetrahydroquinoline by hydrogenation of 6-chloroquinoline after leaving the catalyst prepared in example 3 for 5 months
After the heterogeneous catalyst prepared in example 3 is placed in a cool and shady environment at room temperature and a relative humidity of 70% -80% for 5 months, the catalytic activity of the heterogeneous catalyst is verified according to the following steps: mu.l of 6-chloroquinoline, 10 mg of the catalyst prepared in example 3 after standing for 5 months and 10mL of ethanol were placed in a 50 mL stainless steel autoclave, and after the inside of the stainless steel autoclave was purged with hydrogen 3 times, hydrogen was charged to 1MPa and sealed, and the mixture was heated in a water bath at 60 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 4.45 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the 6-chloroquinoline is 96 percent and the selectivity of the 6-chlorotetrahydroquinoline is 92 percent. By comparing example 16 with example 20, it can be seen that the catalyst obtained in example 3 is very stable and very inert to both air and moisture.
Comparative example 1 is based on TiO2(B) Heterogeneous catalyst loaded with 20% Ru
0.2g TiO was added to a 100mL beaker2(B) And then 8ml of previously prepared RuCl was added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2(B) On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2(B) A supported Ru catalyst.
The TiO obtained in comparative example 1 was aligned by high-resolution Transmission Electron microscope (HRTEM)2(B) Characterization of the supported Ru catalyst confirmed that the catalyst was composed of titanium dioxide and nanometersThe metal Ru is jointly composed. Ru nano particles are uniformly distributed on TiO2(B) On the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. Through counting 150 nanometer Ru metal particles, the average particle size of the Ru nanometer particles is 4.5nm, and a part of large particles are agglomerated.
Mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in comparative example 1 and 10mL of methylene chloride were charged into a 50 mL stainless steel autoclave, and after the inside of the stainless steel autoclave was charged and exhausted with hydrogen 3 times, the inside was charged with hydrogen to 1MPa and sealed, and the mixture was heated in a water bath at 40 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3.0 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating that the conversion rate of the obtained 6-chloroquinoline is 46% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 85%.
Comparative example 2 catalyst based on titanium dioxide P25 loaded with 20% Ru
Preparing a catalyst: 250.2 g of titanium dioxide P are added to a 100ml beaker, followed by 8ml of the previously prepared RuCl3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbed on titanium dioxide P25. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. The solid mixture obtained above was placed in a tube furnace and calcined at 300 ℃ for 1 hour under a hydrogen atmosphere to obtain a P25-supported Ru catalyst.
The Ru catalyst supported on titanium dioxide P25 obtained in comparative example 2 was characterized by a high-resolution transmission electron microscope (HRTEM), and it was confirmed that the catalyst was composed of titanium dioxide and a nano-metal Ru. The Ru nano particles are uniformly distributed on the titanium dioxide P25 material, and the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 5.6nm by counting 150 nanometer Ru metal particles.
Mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in comparative example 2 and 10mL of methylene chloride were charged into a 50 mL stainless steel autoclave, and after the inside of the stainless steel autoclave was charged and exhausted with hydrogen 3 times, the inside was charged with hydrogen to 1MPa and sealed, and the mixture was heated in a water bath at 40 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3.0 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating that the conversion rate of the obtained 6-chloroquinoline is 35% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 80%.
As can be seen from comparative examples 1 and 2, TiO alone2(B) Or when the titanium dioxide P25 is a carrier loaded with 20% of Ru, the Ru nanoparticles of the titanium dioxide P25 become large obviously, the catalytic activity becomes poor obviously, the size of the metal particles is proved to play a crucial role in the reaction, and the oxygen vacancy of the titanium dioxide is further proved to play an important role in controlling the size of the metal nanoparticles.
Comparative example 3 catalyst based on commercial activated carbon loaded Ru for hydrogenation of 6-chloroquinoline to tetrahydro 6-chloroquinoline
Preparing a catalyst: 0.2g of commercial activated carbon (coconut shell activated carbon, 200-300 mesh, available from Jiuding chemical technology Co., Ltd.) was added to 50 mL of deionized water, and 8mL of previously prepared RuCl was added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on activated carbon. Then heating and stirring at 70 ℃ until the deionized water in the beaker is completely volatilized, and obtaining a solid mixture. And (3) placing the prepared solid mixture into a tubular furnace, and calcining the solid mixture for 3 hours at the temperature of 300 ℃ in a hydrogen atmosphere to obtain the Ru catalyst supported by the active carbon.
The Ru catalyst supported by the activated carbon obtained in the comparative example 3 was characterized by a high-resolution transmission electron microscope (HRTEM), and it was confirmed that the catalyst was composed of activated carbon and a nano-metal Ru. The Ru nano particles are uniformly distributed on the activated carbon material. The average grain diameter of the Ru nano particles is 3.8nm by counting 150 nanometer Ru metal particles.
Mu.l of 6-chloroquinoline, 10 mg of the heterogeneous catalyst prepared in comparative example 3 and 10mL of methylene chloride were charged into a 50 mL stainless steel autoclave, and after the inside of the stainless steel autoclave was charged and exhausted with hydrogen 3 times, the inside was charged with hydrogen to 1MPa and sealed, and the mixture was heated in a water bath at 40 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3.0 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating that the conversion rate of the obtained 6-chloroquinoline is 50% and the selectivity of the 1,2,3, 4-tetrahydro 6-chloroquinoline is 85%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (6)
1. A super-dispersed noble metal heterogeneous catalyst is characterized by comprising a titanium dioxide carrier with oxygen vacancies and noble metal particles loaded on the titanium dioxide carrier, wherein the loading amount of the noble metal particles is 10-25%, and the noble metal particles are Au, Ag, Rh, Os, Ir, Ru, Pt or Pd particles, preferably Ru or Pd particles; the average particle diameter of the noble metal particles is 1 to 3 nm.
2. A super-dispersed noble metal heterogeneous catalyst as set forth in claim 1, wherein said titanium dioxide having oxygen vacancies is prepared by the process comprising: with TiO2(B) Calcining the raw materials in an inert gas atmosphere at the temperature of 500-1200 ℃ for 0.5-8 h to obtain the titanium dioxide with the oxygen vacancy.
3. A super-dispersed noble metal heterogeneous catalyst as claimed in claim 2 wherein said inert gas is nitrogen.
4. A super-dispersed noble metal heterogeneous catalyst as claimed in claim 1, wherein said heterogeneous catalyst is prepared by a process comprising the steps of:
1) adding the titanium dioxide with the oxygen vacancy into an aqueous solution of a noble metal precursor, stirring and mixing uniformly to enable the noble metal precursor to be adsorbed on the titanium dioxide, and then heating and stirring at 60-80 ℃ until the moisture is completely volatilized to obtain a solid mixture;
2) placing the solid mixture obtained in the step 1) in a tubular furnace, and roasting in an atmosphere of introducing hydrogen to reduce the precious metal precursor loaded on the titanium dioxide into precious metal particles, thus obtaining the heterogeneous catalyst; the noble metal precursor is chlorine salt or nitrate of Au, Ag, Rh, Os, Ir, Ru, Pt or Pd metal, preferably chlorine salt of Ru or Pd metal.
5. The heterogeneous catalyst according to claim 1, wherein the calcination temperature in step 2) is 200-600 ℃, preferably 250-500 ℃.
6. The application of the noble metal heterogeneous catalyst in the selective hydrogenation of quinoline compounds as claimed in claim 1, wherein the quinoline compounds are mixed with a solvent, and the mixed reaction solution is subjected to selective hydrogenation with hydrogen under the action of the heterogeneous catalyst to generate hydrogenated quinoline compounds; wherein the reaction temperature is 20-100 ℃, and the reaction pressure is 0.5-2 MPa; the solvent is ethanol, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, N-dimethylformamide, N-hexane or toluene.
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| CN113198466A (en) * | 2021-05-14 | 2021-08-03 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of levulinic acid compounds and application of heterogeneous catalyst |
| CN113633820A (en) * | 2021-08-09 | 2021-11-12 | 复旦大学 | Nanowire array and preparation method and application thereof |
| CN114100627A (en) * | 2021-09-29 | 2022-03-01 | 上海工程技术大学 | Method for preparing trimethylhydroquinone by trimethylbenzoquinone |
| CN115282956A (en) * | 2022-08-11 | 2022-11-04 | 台州学院 | Titanium dioxide loaded ruthenium metal catalyst and preparation method and application thereof |
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| CN110937628A (en) * | 2019-12-09 | 2020-03-31 | 浙江工业大学 | TiO with oxygen vacancy2Method for producing a material |
| CN111068669A (en) * | 2020-01-14 | 2020-04-28 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof |
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| CN110937628A (en) * | 2019-12-09 | 2020-03-31 | 浙江工业大学 | TiO with oxygen vacancy2Method for producing a material |
| CN111068669A (en) * | 2020-01-14 | 2020-04-28 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113198466A (en) * | 2021-05-14 | 2021-08-03 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of levulinic acid compounds and application of heterogeneous catalyst |
| CN113198466B (en) * | 2021-05-14 | 2022-04-29 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of levulinic acid compounds and application of heterogeneous catalyst |
| CN113633820A (en) * | 2021-08-09 | 2021-11-12 | 复旦大学 | Nanowire array and preparation method and application thereof |
| CN113633820B (en) * | 2021-08-09 | 2022-10-28 | 复旦大学 | Nanowire array and preparation method and application thereof |
| CN114100627A (en) * | 2021-09-29 | 2022-03-01 | 上海工程技术大学 | Method for preparing trimethylhydroquinone by trimethylbenzoquinone |
| CN115282956A (en) * | 2022-08-11 | 2022-11-04 | 台州学院 | Titanium dioxide loaded ruthenium metal catalyst and preparation method and application thereof |
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