CN110918091B - Application of RuSn alloy cluster composite material - Google Patents
Application of RuSn alloy cluster composite material Download PDFInfo
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- CN110918091B CN110918091B CN201911259811.2A CN201911259811A CN110918091B CN 110918091 B CN110918091 B CN 110918091B CN 201911259811 A CN201911259811 A CN 201911259811A CN 110918091 B CN110918091 B CN 110918091B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 239000000956 alloy Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 157
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 238000011068 loading method Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical group O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical group O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 53
- 230000000694 effects Effects 0.000 abstract description 19
- 239000000243 solution Substances 0.000 description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 238000003756 stirring Methods 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000000967 suction filtration Methods 0.000 description 34
- 238000005406 washing Methods 0.000 description 33
- 239000007789 gas Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 238000001816 cooling Methods 0.000 description 22
- 239000010453 quartz Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 21
- 239000003513 alkali Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000005530 etching Methods 0.000 description 15
- 238000002390 rotary evaporation Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000010431 corundum Substances 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 14
- 239000002086 nanomaterial Substances 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 13
- TTXWERZRUCSUED-UHFFFAOYSA-N [Ru].[Sn] Chemical compound [Ru].[Sn] TTXWERZRUCSUED-UHFFFAOYSA-N 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910001128 Sn alloy Inorganic materials 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 8
- 150000003248 quinolines Chemical class 0.000 description 8
- LBUJPTNKIBCYBY-UHFFFAOYSA-N tetrahydroquinoline Natural products C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 238000003965 capillary gas chromatography Methods 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 229940078552 o-xylene Drugs 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- -1 1,2, 3, 4-tetrahydroquinoline compound Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- GKJSZXGYFJBYRQ-UHFFFAOYSA-N 6-chloroquinoline Chemical compound N1=CC=CC2=CC(Cl)=CC=C21 GKJSZXGYFJBYRQ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011925 1,2-addition Methods 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960001193 diclofenac sodium Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000955 prescription drug Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B01J35/60—
-
- 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
- C07D215/04—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- 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
-
- 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
- C07D215/20—Oxygen atoms
Abstract
The invention provides an application of RuSn alloy cluster composite material in quinoline hydrogenation reaction; the RuSn alloy cluster composite material is formed by sulfur-doped mesoporous carbon and RuSn alloy clusters loaded on the sulfur-doped mesoporous carbon. Experimental results show that the RuSn alloy cluster composite material has higher activity and selectivity when being used as a catalyst for quinoline hydrogenation reaction.
Description
Technical Field
The invention relates to the technical field of quinoline hydrogenation catalysis, in particular to application of RuSn alloy cluster composite material in quinoline hydrogenation reaction.
Background
The 1,2, 3, 4-tetrahydroquinoline compound (py-THQ) is a bioactive skeleton molecule and a key intermediate in the production and manufacturing processes of medicines, alkaloids, agricultural chemicals and other fine chemicals, and the py-THQ exists in some important prescription drugs such as oxanil, nicardiol, vilamycin and diclofenac sodium, so that the synthesis of the py-THQ is very important.
At present, the preparation method of py-THQ comprises catalytic cyclization reaction, beckmann rearrangement reaction and selective hydrogenation reaction of N-containing heterocyclic molecules; among them, the method of obtaining py-THQ by hydrogenating quinoline (containing N heterocyclic molecules) is the most important synthesis method due to the advantages of direct and simple method, high atom utilization rate and the like.
However, the hydrogenation of quinoline also has a number of disadvantages, such as: the hydrogenation reaction of quinoline shows a higher reaction energy barrier, which makes the reaction process inherently sluggish and requires harsh reaction conditions; other intermediates and byproducts may be generated in the reaction process; in the case of quinoline derivatives, especially quinoline derivatives having a readily reducible functional group such as halogen, they may be hydrogenated during the hydrogenation reduction process, thereby reducing the selectivity of the reaction; the strong coordination between the N atoms in the metal and nitrogen heterocyclic molecules poisons the active sites of the catalyst, thereby reducing the stability of the catalyst. Therefore, the choice of a quinoline hydrogenation catalyst is very important.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the application of the RuSn alloy cluster composite material in the quinoline hydrogenation reaction, and the RuSn alloy cluster composite material has higher activity and selectivity in the quinoline hydrogenation reaction as a catalyst.
In view of the above, the present application provides an application of RuSn alloy cluster composite material in quinoline hydrogenation reaction; the RuSn alloy cluster composite material is formed by sulfur-doped mesoporous carbon and RuSn alloy clusters loaded on the sulfur-doped mesoporous carbon.
Preferably, the average particle size of the RuSn alloy cluster in the RuSn alloy cluster composite material is 0.8-1.2 nm.
Preferably, the molar ratio of Ru to Sn in the RuSn alloy cluster composite material is (1-4): 1.
preferably, the total loading of the RuSn alloy clusters in the RuSn alloy cluster composite material is 5-15 wt%.
Preferably, the preparation method of the RuSn alloy cluster composite material specifically comprises the following steps:
mixing sulfur-doped mesoporous carbon, a ruthenium source, a tin source and a solvent to obtain an initial mixture;
and carrying out heat treatment on the initial mixture in a reducing atmosphere to obtain the RuSn alloy cluster composite material.
Preferably, the reducing atmosphere is a hydrogen atmosphere or a hydrogen mixed gas atmosphere, and the hydrogen mixed gas atmosphere is selected from a mixed gas of hydrogen and nitrogen, a mixed gas of hydrogen and argon or a mixed gas of hydrogen and carbon monoxide; the ruthenium source is selected from ruthenium trichloride hydrate, the tin source is selected from stannous chloride dihydrate, and the solvent is deionized water.
Preferably, the heating rate of the heat treatment is 2-20 ℃/min, the temperature is 500-900 ℃, and the time is 1-8 h.
Preferably, the pressure of hydrogen in the quinoline hydrogenation reaction is 1-3 MPa, the temperature is 100-150 ℃, and the time is 0.1-6 h.
Preferably, in the quinoline hydrogenation reaction, the RuSn alloy cluster composite material accounts for 0.04 mol% to 0.3 mol% of the quinoline, based on Ru in the RuSn alloy cluster composite material.
The application provides an application of a RuSn alloy cluster composite material in quinoline hydrogenation reaction, wherein the RuSn alloy cluster composite material is formed by sulfur-doped mesoporous carbon and RuSn alloy clusters loaded on the sulfur-doped mesoporous carbon. The RuSn alloy cluster in the RuSn alloy cluster composite material is an ultra-small alloy cluster, the size of the RuSn alloy cluster composite material is small, the number of exposed active sites is large, and meanwhile, the doping of Sn in the RuSn alloy cluster composite material can induce the electronic structure or the electronic state density of Ru to change so as to have an electronic effect, so that the RuSn alloy cluster provided by the application has high activity and selectivity as a quinoline hydrogenation catalyst. Experimental results show that the RuSn alloy cluster composite material has higher activity and selectivity when being used as a catalyst for quinoline hydrogenation reaction.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of RuSn alloy cluster composite materials synthesized by a part of samples in examples 1-9 of the present invention at different temperatures, different loading amounts and different proportions;
FIG. 2 is an X-ray powder diffraction characterization diagram of a portion of samples provided in examples 1-9 of the present invention including carbon carriers;
FIG. 3 is a chart of high angle annular dark field TEM data and particle size distribution chart for 7 wt% Ru2Sn prepared in example 6 according to the present invention;
FIG. 4 is a line scan characterization map of 7 wt% Ru2Sn prepared according to example 6 of the present invention;
FIG. 5 is a TPR characterization plot of 7 wt% Ru2Sn prepared in example 6 of the present invention;
FIG. 6 is a bar graph of the results of quinoline hydrogenation reaction using different temperature synthesized 5 wt% RuSn alloy cluster composites and commercial ruthenium carbon catalysts prepared in examples 1,2 and 3 of the present invention;
fig. 7 is a bar graph of data of results of hydrogenation reaction of quinoline on the RuSn alloy cluster composite materials with different loading amounts and the commercial ruthenium carbon catalyst prepared in the embodiments 4, 5 and 8 of the present invention;
FIG. 8 is a bar graph of results of hydrogenation reaction of quinoline on RuSn alloy cluster composite materials and commercial ruthenium carbon catalysts prepared in different proportions in examples 6, 7 and 9 of the present invention;
FIG. 9 is a comparison graph of morphology and quinoline hydrogenation activity for example 6 of the present invention and a comparison catalyst;
FIG. 10 is a XPS comparison result graph and a quinoline derivative activity comparison graph of example 6 of the present invention and a comparative monometallic Ru.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The preparation of py-THQ by catalyzing quinoline hydrogenation by using a catalyst is related to a solvent and a carrier of a reaction system, and specifically comprises the following steps: first quinoline is adsorbed on the catalyst surface mainly on the carrier in an inclined direction through hydrogen bonds between the pyridine ring and the carrier, and at the same time, hydrogen can be activated to form active hydrogen on the active sites of the catalyst through hybrid hydrogen cracking or homogeneous hydrogen cracking process, then the activated hydrogen is transferred to quinoline molecules mainly through 1, 2-addition pathway, and 1, 4-addition proceeds to a small extent, and finally, the generated py-THQ rapidly leaves the catalyst surface, is substituted by more strongly bound quinoline molecules, and further hydrogenation to DHQ is avoided. Therefore, quinoline hydrogenation is the hydrogenation of nitrogen heterocycles, and the addition is the addition of an aromatic heterocyclic ring containing an N ═ C double bond and a C ═ C double bond, quinoline is mainly adsorbed on a carrier or a non-noble metal, and the technical problems of quinoline hydrogenation are mainly high reaction energy barrier, certain toxicity of a substrate to a catalyst and the like. In view of the principle and the problem of quinoline hydrogenation, the application provides the application of the RuSn alloy cluster composite material in quinoline hydrogenation reaction; the RuSn alloy cluster composite material is formed by sulfur-doped mesoporous carbon and RuSn alloy clusters loaded on the sulfur-doped mesoporous carbon.
The average particle size of RuSn alloy clusters in the RuSn alloy cluster composite material is 0.8-1.2 nm, and the RuSn alloy clusters are uniformly and stably loaded on the surface of sulfur-doped mesoporous carbon. The small-size RuSn alloy cluster has more exposed active sites and high utilization rate of the active sites; for the hydrogenation of quinolines as catalystsThe reagent increases active site Ru and substrate quinoline and reactant H thereof2Contact and adsorption; the bimetallic system ensures a high selectivity. The molar ratio of Ru to Sn in the RuSn alloy cluster composite material is (1-4): 1. the total loading capacity of the RuSn alloy cluster in the RuSn alloy cluster composite material is 5-15 wt%; in a specific embodiment, the atomic ratio of Ru to Sn is (1-4): 1, the total loading of the RuSn alloy cluster is 6-11 wt%, wherein the loading of Ru is 3-7%.
In the present application, the preparation method of the RuSn alloy cluster composite material specifically comprises:
mixing sulfur-doped mesoporous carbon, a ruthenium source, a tin source and a solvent to obtain an initial mixture;
and carrying out heat treatment on the initial mixture in a reducing atmosphere to obtain the RuSn alloy cluster composite material.
More specifically, the preparation method of the sulfur-doped mesoporous carbon comprises the following steps:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, fully and uniformly stirring, drying and calcining at high temperature to obtain a carbon material; and subsequently, sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
In the preparation process of the sulfur-doped mesoporous carbon, the sulfur-containing organic micromolecules are 2, 2' -bithiophene, and the transition metal salt is selected from cobalt nitrate hexahydrate; the sulfur-containing small molecule, SiO2The molar ratio of the pellets to the transition metal salt is 2:2: 1; the calcining temperature is 600-1200 ℃.
In the above process of preparing the RuSn alloy cluster composite material, the ruthenium source is selected from ruthenium trichloride hydrate, the tin source is selected from stannous chloride dihydrate, and the solvent is deionized water. The reducing atmosphere is hydrogen atmosphere or hydrogen mixed gas atmosphere, and the hydrogen mixed gas atmosphere is selected from mixed gas of hydrogen and nitrogen, mixed gas of hydrogen and argon or mixed gas of hydrogen and carbon monoxide. The heating rate of the heat treatment is 2-20 ℃/min, the temperature is 500-900 ℃, and the time is 1-8 h.
The sulfur-doped mesoporous carbon has a good metal fixing effect, and can provide enough anchor points for the alloy clusters, so that the sintering and agglomeration of ultra-small ruthenium-tin alloy clusters in the reduction calcination process are inhibited, and the sulfur-doped mesoporous carbon is stably loaded on the surface of the sulfur-doped mesoporous carbon.
The specific reaction system of the application of the RuSn alloy cluster composite material in the quinoline hydrogenation reaction is as follows:
reacting quinoline, RuSn alloy cluster composite material and hydrogen in a closed container.
In the above process, the quinoline is quinoline in a broad range well known to those skilled in the art, and includes quinoline derivatives having a halogen. The pressure of hydrogen for quinoline hydrogenation is 1-3 MPa, the reaction temperature is 100-150 ℃, and the time is 0.1-6 h. And the RuSn alloy cluster composite material accounts for 0.04 mol% -0.3 mol% of the quinoline based on Ru in the RuSn alloy cluster composite material.
For further understanding of the present invention, the following examples are given to illustrate the application of the RuSn alloy cluster composite material in the quinoline hydrogenation reaction, and the scope of the present invention is not limited by the following examples.
Example 1
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml of tetrahydrofuran, stirring for about 12 hours to reach a uniform state, and then removing the tetrahydrofuran solvent by a rotary evaporation method to obtain a dry uniform mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then naturally cooling to the room temperature, and keeping the pressure in the tubular furnace at normal pressure during the temperature raising and cooling period; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); the solid obtained by suction filtration is transferred into a flask again, and NaOH solution with the concentration of 2mol/L is addedAbout 100mL of the solution is mixed and stirred for 36 hours for the second alkali etching; performing suction filtration again and washing until the solution is neutral (washing the solution for more than three times by deionized water), placing the solution in a 250ml round-bottom flask, adding 120ml of sulfuric acid solution with the concentration of 0.5mol/L, performing oil bath at the temperature of 90 ℃, refluxing for 12 hours, performing suction filtration and washing (washing the solution for more than three times by deionized water) until the solution is neutral, and placing the obtained sample in an oven (60 ℃) for 8-12 hours to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 44.56mg of the sulfur-doped mesoporous carbon nano material S-C and RuCl containing 2.5mg of Ru3And 2.936mgSn of SnCl2(the atomic ratio of Ru/Sn is ensured to be 1, meanwhile, the loading amount of Ru is 5%, and the total loading amount is 10.87%) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept at 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 600 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% RuSn/SC-600 ℃.
d. The specific process of quinoline hydrogenation: in a stainless steel autoclave equipped with a manometer, the molar weight ratio of quinoline to Ru in the above RuSn/SC catalyst was 1000: 3, respectively adding 1mmol of quinoline, 6.06mg of 5% RuSn/SC-600 ℃ catalyst and 1mL of ethanol; after the autoclave is sealed, firstly, filling and discharging five times by using hydrogen as filling gas, and then pressurizing to 1Mpa by using the hydrogen at room temperature; then heating to 100 ℃, magnetically stirring under the condition, and reacting for 1 h; after the reaction, the reaction kettle is immediately cooled to room temperature by cold water, the product is diluted by ethyl acetate (10ml) after centrifugal separation, and quantitative analysis is carried out by adopting a capillary column gas chromatography with o-xylene as an internal standard substance.
Example 2
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml tetrahydrofuran, stirring for about 12h to obtain uniform state, and removing tetrahydrofuran solvent by rotary evaporation to obtain dried productA homogeneous mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then naturally cooling to the room temperature, and keeping the pressure in the tubular furnace at normal pressure during the temperature raising and cooling period; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); transferring the solid obtained by suction filtration into the flask again, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 36h to carry out secondary alkali etching; performing suction filtration again and washing until the solution is neutral (washing with deionized water for more than three times), placing the solution in a 250ml round-bottom flask, adding 120ml of sulfuric acid solution with the concentration of 0.5mol/L, performing oil bath at the temperature of 90 ℃, refluxing for 12 hours, performing suction filtration and washing (washing with deionized water for more than three times) until the solution is neutral, and placing the obtained sample in an oven (60 ℃) for 8-12 hours to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 44.56mg of the sulfur-doped mesoporous carbon nano material S-C and RuCl containing 2.5mg of Ru3And 2.936mgSn of SnCl2(the atomic ratio of Ru/Sn is ensured to be 1, meanwhile, the loading amount of Ru is 5%, and the total loading amount is 10.87%) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept at 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% RuSn/SC-700 ℃.
d. The specific process of quinoline hydrogenation: in a stainless steel autoclave equipped with a manometer, the molar weight ratio of quinoline to Ru in the above RuSn/SC catalyst was 1000: 3, respectively adding 1mmol of quinoline, 6.06mg of 5% RuSn/SC-700 ℃ catalyst and 1mL of ethanol; after the autoclave is sealed, firstly, filling and discharging five times by using hydrogen as filling gas, and then pressurizing to 1Mpa by using the hydrogen at room temperature; then heating to 100 ℃, magnetically stirring under the condition, and reacting for 1 h; after the reaction, the reaction kettle is immediately cooled to room temperature by cold water, the product is diluted by ethyl acetate (10ml) after centrifugal separation, and quantitative analysis is carried out by adopting a capillary column gas chromatography with o-xylene as an internal standard substance.
Example 3
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml of tetrahydrofuran, stirring for about 12 hours to reach a uniform state, and then removing the tetrahydrofuran solvent by a rotary evaporation method to obtain a dry uniform mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then naturally cooling to the room temperature, and keeping the pressure in the tubular furnace at normal pressure during the temperature raising and cooling period; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); transferring the solid obtained by suction filtration into the flask again, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 36h to carry out secondary alkali etching; performing suction filtration again and washing until the solution is neutral (washing with deionized water for more than three times), placing the solution in a 250ml round-bottom flask, adding 120ml of sulfuric acid solution with the concentration of 0.5mol/L, performing oil bath at the temperature of 90 ℃, refluxing for 12 hours, performing suction filtration and washing (washing with deionized water for more than three times) until the solution is neutral, and placing the obtained sample in an oven (60 ℃) for 8-12 hours to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 44.56mg of the sulfur-doped mesoporous carbon nano material S-C and RuCl containing 2.5mg of Ru3And 2.936mgSn of SnCl2(the atomic ratio of Ru/Sn is ensured to be 1, meanwhile, the loading amount of Ru is 5%, and the total loading amount is 10.87%) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept at 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% RuSn/SC-800 ℃.
d. The specific process of quinoline hydrogenation: in a stainless steel autoclave equipped with a manometer, the molar weight ratio of quinoline to Ru in the above RuSn/SC catalyst was 1000: 3, respectively adding 1mmol of quinoline, 6.06mg of 5% RuSn/SC-800 ℃ catalyst and 1mL of ethanol; after the autoclave is sealed, firstly, filling and discharging five times by using hydrogen as filling gas, and then pressurizing to 1Mpa by using the hydrogen at room temperature; then heating to 100 ℃, magnetically stirring under the condition, and reacting for 1 h; after the reaction, the reaction kettle is immediately cooled to room temperature by cold water, the product is diluted by ethyl acetate (10ml) after centrifugal separation, and quantitative analysis is carried out by adopting a capillary column gas chromatography with o-xylene as an internal standard substance.
Example 4
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml of tetrahydrofuran, stirring for about 12 hours to reach a uniform state, and then removing the tetrahydrofuran solvent by a rotary evaporation method to obtain a dry uniform mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then naturally cooling to the room temperature, and keeping the pressure in the tubular furnace at normal pressure during the temperature raising and cooling period; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); transferring the solid obtained by suction filtration into the flask again, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 36h to carry out secondary alkali etching; after the solution is filtered again and washed to neutrality (more than three times by deionized water flushing), the solution is placed in a 250ml round-bottom flask, and 120ml of sulfuric acid solution with the concentration of 0.5mol/L is addedCarrying out oil bath at the temperature of 90 ℃, refluxing for 12h, then carrying out suction filtration washing (washing with deionized water for more than three times) until the solution is neutral, and placing the obtained sample in an oven (at 60 ℃) for 8-12h to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 46.74mg of the sulfur-doped mesoporous carbon nanomaterial S-C and RuCl containing 1.5mg of Ru3And 1.76mgSn of SnCl2(the atomic ratio of Ru/Sn is ensured to be 1, meanwhile, the loading capacity of Ru is 3 percent, and the total loading capacity is 6.52 percent) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept to be 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 3 wt% RuSn/SC-700 ℃.
d. The specific process of quinoline hydrogenation: in a stainless steel autoclave equipped with a manometer, the ratio of the molar amount of quinoline to Ru in the above RuSn/SC catalyst was 1000: 1.5, adding 1mmol of quinoline and 5.05mg of 3% RuSn/SC-700 ℃ catalyst and 1mL of ethanol respectively; after the autoclave was sealed, the autoclave was first charged and discharged five times with hydrogen as a filling gas, and then pressurized to 1mpa with hydrogen at room temperature; then heating to 100 ℃, magnetically stirring under the condition, and reacting for 1 h; after the reaction was completed, the reaction vessel was immediately cooled to room temperature with cold water. The product was centrifuged and diluted with ethyl acetate (10ml) and quantitatively analyzed by capillary column gas chromatography using o-xylene as an internal standard.
Example 5
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml of tetrahydrofuran, stirring for about 12 hours to reach a uniform state, and then removing the tetrahydrofuran solvent by a rotary evaporation method to obtain a dry uniform mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, placing the quartz crucible or the corundum crucible into a tube furnace, introducing nitrogen as protective gas, raising the temperature of the tube furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, and heating the tube furnace at the temperatureNaturally cooling to room temperature after keeping for 2h, and keeping normal pressure in the tubular furnace during the period of heating and cooling; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); transferring the solid obtained by suction filtration into the flask again, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 36h to carry out secondary alkali etching; performing suction filtration again and washing until the solution is neutral (washing the solution for more than three times by deionized water), placing the solution in a 250ml round-bottom flask, adding 120ml of sulfuric acid solution with the concentration of 0.5mol/L, performing oil bath at the temperature of 90 ℃, refluxing for 12 hours, performing suction filtration and washing (washing the solution for more than three times by deionized water) until the solution is neutral, and placing the obtained sample in an oven (60 ℃) for 8-12 hours to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 42.39mg of the sulfur-doped mesoporous carbon nano material S-C and RuCl containing 3.5mg of Ru3And SnCl of 4.11mgSn2(the atomic ratio of Ru/Sn is ensured to be 1, meanwhile, the loading amount of Ru is 7 percent, and the total loading amount is 15.2 percent) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept to be 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, introducing 5% vol H2/Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2.0H; naturally cooling to room temperature to obtain 7 wt% RuSn/SC-700 ℃.
d. The specific process of quinoline hydrogenation: in a stainless steel autoclave equipped with a manometer, the ratio of the molar amount of quinoline to Ru in the above RuSn/SC catalyst was 1000: 1.5, adding 1mmol of quinoline and 2.17mg of 7% RuSn/SC-700 ℃ catalyst and 1mL of ethanol respectively; after the autoclave was sealed, the autoclave was first charged and discharged five times with hydrogen as a filling gas, and then pressurized to 1mpa with hydrogen at room temperature; then heating to 100 ℃, magnetically stirring under the condition, and reacting for 1 h; after the reaction was completed, the reaction vessel was immediately cooled to room temperature with cold water. The product was centrifuged and diluted with ethyl acetate (10ml) and quantitatively analyzed by capillary column gas chromatography using o-xylene as an internal standard.
Example 6
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml of tetrahydrofuran, stirring for about 12 hours to reach a uniform state, and then removing the tetrahydrofuran solvent by a rotary evaporation method to obtain a dry uniform mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then naturally cooling to the room temperature, and keeping the pressure in the tubular furnace at normal pressure during the temperature raising and cooling period; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); transferring the solid obtained by suction filtration into the flask again, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 36h to carry out secondary alkali etching; performing suction filtration again and washing until the solution is neutral (washing the solution for more than three times by deionized water), placing the solution in a 250ml round-bottom flask, adding 120ml of sulfuric acid solution with the concentration of 0.5mol/L, performing oil bath at the temperature of 90 ℃, refluxing for 12 hours, performing suction filtration and washing (washing the solution for more than three times by deionized water) until the solution is neutral, and placing the obtained sample in an oven (60 ℃) for 8-12 hours to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 44.44mg of the sulfur-doped mesoporous carbon nano material S-C and RuCl containing 3.5mg of Ru3And 2.06mgSn of SnCl2(ensuring that the atomic ratio of Ru/Sn is 2, the loading amount of Ru is 7% and the total loading amount is 11.12%) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept at 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, introducing 5% vol H2/Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2.0H; naturally cooling to room temperature to obtain 7 wt% Ru2Sn/SC-700 ℃.
d. The specific process of quinoline hydrogenation: quinoline and a 7% Ru2Sn/SC-700 ℃ catalyst and 1mL of ethanol are respectively added into a stainless steel autoclave provided with a pressure gauge; after the autoclave is sealed, firstly, filling and discharging five times by using hydrogen as filling gas, and then pressurizing by using hydrogen at room temperature; then heating, magnetically stirring under the condition, and reacting; after the reaction was completed, the reaction vessel was immediately cooled to room temperature with cold water. The product was centrifuged and diluted with ethyl acetate (10ml) and quantitatively analyzed by capillary column gas chromatography using o-xylene as an internal standard.
Example 7
a. 1g of bithiophene, 1g of SiO2Pellets (particle size 7nm), 0.5g Co (NO)3)2·6H2Mixing O with 120ml of tetrahydrofuran, stirring for about 12 hours to reach a uniform state, and then removing the tetrahydrofuran solvent by a rotary evaporation method to obtain a dry uniform mixture; transferring the obtained mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then naturally cooling to the room temperature, and keeping the pressure in the tubular furnace at normal pressure during the temperature raising and cooling period; then transferring the obtained sample into a flask, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 48 hours to carry out primary alkali etching; then transferring the mixture into a common suction filtration device for suction filtration to remove alkali liquor (only washing once by deionized water); transferring the solid obtained by suction filtration into the flask again, adding about 100mL of NaOH solution with the concentration of 2mol/L, mixing and stirring for 36h to carry out secondary alkali etching; performing suction filtration again and washing until the solution is neutral (washing the solution for more than three times by deionized water), placing the solution in a 250ml round-bottom flask, adding 120ml of sulfuric acid solution with the concentration of 0.5mol/L, performing oil bath at the temperature of 90 ℃, refluxing for 12 hours, performing suction filtration and washing (washing the solution for more than three times by deionized water) until the solution is neutral, and placing the obtained sample in an oven (60 ℃) for 8-12 hours to obtain the sulfur-doped mesoporous carbon nanomaterial;
b. 45.47mg of the sulfur-doped mesoporous carbon nano material S-C and RuCl containing 3.5mg of Ru3And 1.SnCl of 03mgSn2(ensuring that the atomic ratio of Ru/Sn is 4, the loading amount of Ru is 7% and the total loading amount is 9.06%) is placed in a 100mL round-bottom flask, and water is added for dilution (the total volume is kept at 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, introducing 5% vol H2/Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2.0H; naturally cooling to room temperature to obtain 7 wt% Ru4Sn/SC-700 ℃.
d. The specific process of quinoline hydrogenation: in a stainless steel autoclave equipped with a manometer, the ratio of the molar amount of quinoline to Ru in the above RuSn/SC catalyst was 1000: 1.5, 1mmol of quinoline and 2.17mg of 7% Ru4Sn/SC-700 ℃ catalyst and 1mL of ethanol are added respectively; after the autoclave was sealed, the autoclave was first charged and discharged five times with hydrogen as a filling gas, and then pressurized to 1mpa with hydrogen at room temperature; then heating to 100 ℃, magnetically stirring under the condition, and reacting for 45 min; after the reaction was completed, the reaction vessel was immediately cooled to room temperature with cold water. The product was centrifuged and diluted with ethyl acetate (10ml) and quantitatively analyzed by capillary column gas chromatography using o-xylene as an internal standard.
Example 8
The preparation process of example 8 is identical to that of example 2, and only when the quinoline hydrogenation catalytic reaction is specifically carried out, the differences are as follows: the catalyst dosage is reduced by half, and the rest is unchanged.
Example 9
The preparation process of example 9 is identical to that of example 5, and only when the quinoline hydrogenation catalytic reaction is specifically carried out, the differences are as follows: the reaction time was reduced to 45min, the rest being unchanged.
Comparative example 1 (comparative catalyst of example 6)
a. 44.44mg of a commercial mesoporous carbon support Vulcan XC-72R with RuCl containing 3.5mg Ru3And 2.06mgSn of SnCl2(ensuring that the atomic ratio of Ru/Sn is 2, the loading of Ru is 7% and the total loading is 11.1%) is placed in a 100mL round-bottom flask, and water is added to dilute (the total volume is kept at-50 mL) to obtain a mixtureA compound; after the mixture is subjected to ultrasonic treatment for 2 hours, stirring for 12 hours, and performing rotary evaporation to obtain a comparative catalyst-1;
c. putting the obtained comparative catalyst-1 into a quartz boat, introducing 5% vol H2/Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2.0H; naturally cooling to room temperature to obtain the comparative catalyst of 7 wt% Ru2Sn/Vulcan XC-72R-700 ℃.
The commercial catalyst referred to in this application was a commercial ruthenium on carbon catalyst purchased from Alfa Aesar loaded with only the single metal Ru at a loading of 5 wt%.
FIG. 1 is a TEM image of Ru-Sn alloy clusters obtained in examples 1-9 of the present invention at different temperatures in examples 2, 3, 5, 6 and 7; it can be seen from the figure that all the RuSn alloy clusters prepared under different conditions of temperature, loading and ruthenium-tin ratio are ultra-small in size and uniformly distributed.
Fig. 2 is an X-ray powder diffraction characterization of samples prepared in examples 2 and 4 to 7 of examples 1 to 9 of the present invention, including carbon carriers, wherein all the samples have no obvious diffraction peak, and further prove that the particle size of the synthesized material is extremely small and is below the X-ray detection limit, and the 44 ° peak of the sample is shifted with respect to the single metal Ru, thereby illustrating that Ru and Sn are alloyed.
Fig. 3 is a data graph of 7 wt% Ru2Sn under a high-angle annular dark-field transmission electron microscope and a particle size distribution table provided in example 6 of the present invention, and it is clearly seen that the synthesized particle size is only 1.1nm, further proving that the particle size of the synthesized material is extremely small.
FIG. 4 is a line scan characterization chart of 7 wt% Ru2Sn provided in example 6 of the present invention, which shows that a single particle contains both Ru and Sn signals, and that Ru and Sn are alloyed well.
FIG. 5 is a TPR characterization plot of 7 wt% Ru2Sn provided in example 6 of the present invention, showing a shift in the reduction peak toward lower temperatures compared to Sn alone, indicating the occurrence of the H-flooding effect, and also demonstrating ruthenium-tin alloying.
FIG. 6 is a bar graph of the results of quinoline hydrogenation reaction using 5 wt% RuSn and commercial catalyst synthesized at different temperatures provided in examples 1,2 and 3 of the present invention, wherein the samples prepared in the examples of the present application all exhibit certain activity for the quinoline hydrogenation reaction, and the optimal reduction temperature is 700 deg.C; and all have better catalytic activity than commercial catalysts.
Fig. 7 is a histogram of data of results of hydrogenation reaction on quinoline of ruthenium-tin alloys and commercial catalysts with different loading amounts provided in example 8, example 4, and example 5 of the present invention, where the catalysts prepared in the above examples of the present application all exhibit better activity on hydrogenation reaction on quinoline even under more severe reaction conditions, and the optimal loading amount of ruthenium is 7%; and all have better catalytic activity than commercial catalysts.
Fig. 8 is a bar graph of data of results of hydrogenation reaction of quinoline on ruthenium catalyst of ruthenium-tin alloy clusters with different ratios provided in examples 9, 6 and 7 of the present invention, comparing the activities of all samples with commercial ruthenium catalyst, and the optimum ratio of ruthenium-tin is 2:1 (example 6 reaction conditions for quinoline hydrogenation reaction: pressure 1MPa H2And n (catalyst)/n (quinoline) ═ 0.15%, the reaction temperature was 100 ℃ and the reaction time was 45 min.
Fig. 9 is a data graph and a particle size distribution table of the ruthenium-tin alloy cluster composite material and the comparative ruthenium-tin alloy catalyst thereof under a high-angle annular dark-field transmission electron microscope, where the particle size of the ruthenium-tin alloy cluster provided in example 6 is significantly smaller than that of the comparative catalyst thereof, and the XRD graph also confirms the size difference; in addition, FIG. 9 also includes a graph of the kinetic reaction data of the two catalysts for the quinoline hydrogenation reaction, and it is evident that the small particle size of example 6 is far more active than the large particle size of the comparative catalyst, thus indicating that the small particle sample is more active due to the size effect (example 6 reaction conditions for the quinoline hydrogenation reaction: pressure of 1MPa H: pressure)2And n (catalyst)/n (quinoline) is 0.0375%, the reaction temperature is 100 ℃, and the reaction time is 21 h).
FIG. 10 shows data of X-ray photoelectron spectroscopy (XPS) and quinoline derivative activity of a ruthenium-tin alloy cluster composite and a single-metal commercial ruthenium catalyst according to example 6 of the present inventionThe comparison graph corresponds to a spectrogram of Ru3p3/2, and the spectrogram result shows that the electronic structure of the metal Ru with catalytic activity is obviously changed by the incorporation of tin; according to the quinoline derivative activity comparison chart, the selectivity difference of the two catalysts on the 6-chloroquinoline hydrogenation reaction shows that the source of the excellent selectivity of the ruthenium-tin alloy cluster composite material system prepared by the method is the ligand effect (the reaction condition of the 6-chloroquinoline hydrogenation catalytic reaction is that the pressure is 3MPa H2The reaction temperature was 110 ℃ and the reaction time was 6 hours, with n (catalyst)/n (6-chloroquinoline) ═ 0.15%.
Example 10
The RuSn alloy cluster composite material prepared in example 6 is used for quinoline derivative hydrogenation, and the reaction raw materials and effect data are shown in table 1:
TABLE 1 feed and Effect data for quinoline hydrogenation
Note: a.C/S is 0.15 mole%, T is 100 ℃, P is 1 Mpa;
b.C/S＝0.15mole％，T＝120℃，P＝2Mpa；
c.C/S＝0.3mole％，T＝120℃，P＝2Mpa；
C/S stands for catalyst (calculated as Ru)/quinoline.
Example 11
The RuSn alloy cluster composite material prepared in example 6 was compared with the activity of the existing catalyst system, and the results are shown in table 2;
TABLE 2 data table of conditions and effects of quinoline hydrogenation reaction in different systems
Note: TOF ═ the molar amount of quinoline participating in the reaction/the molar amount of catalyst-reaction time (in hours); the TOF value in example 6 is a result calculated from the value obtained in the reaction time of 5min because the substrate conversion rate is less than 50% in 5min, at which time the calculated value is more accurate in the performance of the reaction catalyst.
As can be seen from table 2, the RuSn alloy cluster system shows significantly superior catalytic activity for the hydrogenation reaction of quinoline compared to other catalyst systems.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
- The application of the RuSn alloy cluster composite material in quinoline hydrogenation reaction; the RuSn alloy cluster composite material is formed by sulfur-doped mesoporous carbon and RuSn alloy clusters loaded on the sulfur-doped mesoporous carbon;the average particle size of the RuSn alloy cluster in the RuSn alloy cluster composite material is 0.8-1.2 nm;the molar ratio of Ru to Sn in the RuSn alloy cluster composite material is (1-4): 1.
- 2. the use according to claim 1, wherein the total loading of the RuSn alloy clusters in the RuSn alloy cluster composite material is 5 to 15 wt%.
- 3. The application of claim 1, wherein the preparation method of the RuSn alloy cluster composite material specifically comprises:mixing sulfur-doped mesoporous carbon, a ruthenium source, a tin source and a solvent to obtain an initial mixture;and carrying out heat treatment on the initial mixture in a reducing atmosphere to obtain the RuSn alloy cluster composite material.
- 4. The use according to claim 3, wherein the reducing atmosphere is a hydrogen atmosphere or a hydrogen gas mixture atmosphere selected from a mixture of hydrogen and nitrogen, a mixture of hydrogen and argon, or a mixture of hydrogen and carbon monoxide; the ruthenium source is selected from ruthenium trichloride hydrate, the tin source is selected from stannous chloride dihydrate, and the solvent is deionized water.
- 5. The use according to claim 3, wherein the heat treatment has a temperature rise rate of 2-20 ℃/min, a temperature of 500-900 ℃ and a time of 1-8 h.
- 6. The application of claim 1, wherein the pressure of hydrogen in the quinoline hydrogenation reaction is 1-3 MPa, the temperature is 100-150 ℃, and the time is 0.1-6 h.
- 7. The use according to claim 1, wherein the Rusn alloy cluster composite is present in the quinoline hydrogenation reaction at 0.04 mol% to 0.3 mol% of the quinoline, based on the Ru in the RuSn alloy cluster composite.
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| CN101544601A (en) * | 2009-04-23 | 2009-09-30 | 浙江大学 | Method for synthesizing 5,6,7,8-tetrahydroquinoline |
| CN106432072A (en) * | 2016-09-23 | 2017-02-22 | 大连理工大学 | Preparation method of substituted 1,2,3,4-tetrahydroquinoline |
| CN109759133A (en) * | 2019-02-21 | 2019-05-17 | 中国科学技术大学 | Composite material, preparation method and its application of atom dispersion |
| CN110064423A (en) * | 2019-02-21 | 2019-07-30 | 中国科学技术大学 | Extra small multicomponent alloy composite material, preparation method and its application |
| CN110465297A (en) * | 2019-08-27 | 2019-11-19 | 江西理工大学 | A kind of quinoline adds the preparation method of the multi-element metal nanocatalyst of hydrogen |
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| CN101544601A (en) * | 2009-04-23 | 2009-09-30 | 浙江大学 | Method for synthesizing 5,6,7,8-tetrahydroquinoline |
| CN106432072A (en) * | 2016-09-23 | 2017-02-22 | 大连理工大学 | Preparation method of substituted 1,2,3,4-tetrahydroquinoline |
| CN109759133A (en) * | 2019-02-21 | 2019-05-17 | 中国科学技术大学 | Composite material, preparation method and its application of atom dispersion |
| CN110064423A (en) * | 2019-02-21 | 2019-07-30 | 中国科学技术大学 | Extra small multicomponent alloy composite material, preparation method and its application |
| CN110465297A (en) * | 2019-08-27 | 2019-11-19 | 江西理工大学 | A kind of quinoline adds the preparation method of the multi-element metal nanocatalyst of hydrogen |
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