CN110420669A - Cu cluster preparation method and catalysis CO2React purposes - Google Patents
Cu cluster preparation method and catalysis CO2React purposes Download PDFInfo
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- CN110420669A CN110420669A CN201910526396.6A CN201910526396A CN110420669A CN 110420669 A CN110420669 A CN 110420669A CN 201910526396 A CN201910526396 A CN 201910526396A CN 110420669 A CN110420669 A CN 110420669A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title claims description 26
- 239000010949 copper Substances 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 66
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 10
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- -1 hydrogen furans Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0222—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
One kind being used for catalyzed conversion CO2The carried copper cluster catalyst of basic chemical processed, gold atom number is 24 in Cu cluster, mass content are as follows: X wt%~XX wt%, carrier are transition metal oxide.The beneficial effects of the present invention are: it is reactant using common mantoquita and organic amine, and metal oxide carrier, pass through chemical coordination and reduction, and ultrasonic carrying method, above-mentioned carried copper cluster catalyst material is prepared, copper content is adjustable in a certain range, and different catalytic properties can be had by loading different carriers, for example, the carried copper cluster catalyst material is in catalyzed conversion CO2Excellent catalytic performance is shown in terms of basic chemical processed.The material has many advantages, such as, can be through industrial mass production.The content of copper is few in inventive method catalyst, high-efficient, at low cost, and environmental pollution is small.The invention discloses its preparation methods.
Description
Technical field:
The present invention relates to it is a kind of for carried copper cluster catalyst material and preparation method thereof and its turn in catalysis
Change the application in the reaction of CO2 basic chemical.
Background technique:
Due to a large amount of uses of fossil fuel, the gas concentration lwevel presentation in atmosphere year by year grind by raised situation, correlation
Study carefully and has shown since the industrial revolution, CO in atmosphere2Concentration rises to 355ppm from 280ppm.CO2Cause greenhouse effects
One of predominant gas, CO2It is discharged into atmosphere too much and serious influence is produced on global environment.Pass through renewable energy
Obtained H2With CO2Reaction generates basic chemical, and CO2 is made to get utilization, this can not only alleviate greenhouse effects, also
It can be reduced the dependence in chemical industry production for petroleum resources.Due to CO2Molecule more inertia, industrially uses at present
The reaction condition of Cu/ZnO/Al2O3 catalyst be high temperature and pressure, reaction temperature be 200~300 DEG C, reaction pressure be 50~
100bar, excessive investment reduces economic benefit in energy consumption, not only unfriendly to environment, but also limits CO2 and add hydrogen anti-
The popularization answered.
Currently, have the metal atomic cluster for determining atom number and precision architecture, the behavior of similar molecule and special is presented
Electronic property, when with its peripheral ligand collectively as catalyst, be a kind of structure between homogeneously between multiphase accurately
New catalyst can really reflect influence of the catalyst structure to its performance from atomic level, provide more for catalyticing research
The clear information of essence, is of great significance to the accurate correlation of structure and catalytic performance.In addition to this, traditional catalysis is compared
Agent, metal atomic cluster is smaller, and exposed active site is more, has higher Atom economy, is a kind of ideal green
Color catalysis material.
Therefore, load type gold cluster catalyst material has attracted people widely to close as a kind of novel catalysis material
Note.Largely document report relevant to load type gold cluster catalyst materials synthesis and patent application be constantly published and
It is open.For example, 2018, delivered on Colloids and Surfaces A one of Guangdong University of Technology's Yu Lin topic group
The reduction reaction for being used to be catalyzed 4- nitrophenol using iron oxide loaded Cu cluster is reported in article；2017, Taiyuan science and engineering
Utilization is reported in the article that university's Wang Baojun topic group is delivered on Applied Catalysis A:General
Cu cluster is used for catalyzing acetylene selective hydrogenation；
The result by references for many years about the preparation of carried copper cluster catalyst material is summarized, it can be found that not yet
A kind of method prepare carried copper cluster catalyst material a kind of that copper atom number is controllable and that content is controllable and its
Application in the reaction of catalyzed conversion CO2 basic chemical.
Summary of the invention:
Technical scheme is as follows:
One kind being used for catalyzed conversion CO2The carried copper cluster catalyst of basic chemical processed, which is characterized in that described
Catalyst is the Cu cluster that atom number is 6, mass content are as follows: 0.1wt%~10wt%.
One kind being used for catalyzed conversion CO2The preparation method of the carried copper cluster catalyst of basic chemical processed, it is wrapped
Include following steps:
Step 1 prepares the solution that mass fraction is 0.1%~0.5% mantoquita；
Step 2, the solution for preparing the sodium borohydride (NaBH4) that mass fraction is 0.1%~0.3%；
The 2- mercaptobenzoxazole that quality is 0.6 times of mantoquita quality is added into the solution of step 1 for step 3
(C7H5NOS)；
Step 4, by solution obtained in step 3, be added in the solution of the sodium borohydride in step 2 (NaBH4), and
Stirring is placed 3 hours at 25 DEG C.
Step 5 will obtain mixture by rotary evaporation removing acetonitrile solvent in step 4, remaining solid is washed with ether
It washs, product is extracted with dichloromethane later, obtain [the Cu with precision architecture6(C7H4NOS)6]2-.(cluster is abbreviated as
Cu6)。
Step 6, by Cu obtained in step 5n, a certain amount of oxide (MO) carrier is added, is placed in Ultrasound Instrument 15 points
Zhong Hou, being stirred overnight makes its aging, and the Cu cluster for being 6 using atom number after dry out solvent is the supported catalyst in activated centre
Agent (Cu6/MO)。
Mantoquita described in step 1 is acetylacetone copper or copper nitrate.
Sodium borohydride solution described in step 2 is one kind of water, methanol, ethyl alcohol, isopropanol or butanol.
Organic solvent described in step 5 is methylene chloride, toluene, acetone, acetonitrile, ether, dimethylformamide or four
One of hydrogen furans.
Oxide carrier described in step 6 be silica, aluminium oxide, magnesia, zirconium oxide, titanium oxide, molybdenum oxide,
One of zinc oxide or cobalt oxide.
It is a kind of for being catalyzed the application method of the catalyst of carbon dioxide hydrogenation reaction, which is characterized in that be catalyzed reaction
Temperature is 100~150 DEG C, and pressure is 1~4MPa；Reaction gas CO2:H2:N2 is wherein this H2:CO2=1~3, N2As interior
Mark.
Detailed description of the invention:
Fig. 1 is the UV-Vis spectrogram of Cu metal atomic cluster prepared in the embodiment of the present invention 1.
Fig. 2 is Cu prepared in the embodiment of the present invention 26/ZrO2IR spectrogram.
Fig. 3 is catalyst carbon dioxide hydrogenation reaction result figure prepared in the embodiment of the present invention 2 and 3.
Fig. 4 is the XPS spectrum figure of catalyst prepared in the embodiment of the present invention 4.
Fig. 5 is the TEM transmission electron microscope photo of prepared catalyst prepared in the embodiment of the present invention 5.
Fig. 6 is the XANES spectrogram of the prepared prepared catalyst prepared in the embodiment of the present invention 6.
Specific embodiment:
The present invention is further illustrated with reference to embodiments.
Embodiment 1:
Under constant stirring in by 11.9mg acetylacetone copper (Cu (C5H7O2)2) be added 7.2mL acetonitrile mixed in flask
10min.Then by the 2- mercaptobenzoxazole (C of 7.12mg7H5NOS above-mentioned solution) is added, is stirred to react 15 minutes.Meanwhile In
By 10.8mg NaBH in 1 hour4It is dissolved in acetonitrile.Then, above two solution is mixed in flask, and at 25 DEG C
Stirring is placed 3 hours.Acetonitrile solvent is removed by rotary evaporation, obtained solid is washed with ether, it is unreacted to remove
Mercaptan and possible disulfide by-products.Then product is extracted with dichloromethane, obtains [the Cu with precision architecture6
(C7H4NOS)6]2-(it is abbreviated as Cu6).It is tested by ultraviolet-visible spectrum (UV-Vis), obtained Cu cluster is Cu6, see
Fig. 1.Take 15 milligrams of Cu6500 milligrams of ZrO are added2, it is placed in Ultrasound Instrument after 15 minutes, being stirred overnight makes its aging, dry out solvent
The Cu cluster for being afterwards 6 using atom number is the loaded catalyst (Cu in activated centre6/ZrO2).Wherein Cu content is 0.8%.
Catalytic reaction condition are as follows: the temperature of preferred catalytic reaction is 130 degree, pressure 2MPa；Reaction gas is CO2:H2:N2,
Wherein H2:CO2=3, N2As internal standard.Under this condition, 100 are put into the autoclave with polytetrafluoroethyllining lining
Milligram catalyst, carbon dioxide is under the catalytic action of catalyst by hydrogen reducing to organic matter, after reaction 10 hours, titanium dioxide
Efficiency of carbon con version 3.6%, wherein the selectivity of methanol is 36%, methyl formate 64%.Catalytic performance is shown in Fig. 3.
Embodiment 2:
Under constant stirring in by 8.52mg copper nitrate (Cu (NO3)2) be added 7.2mL acetonitrile 10min is mixed in flask.
Then by the 2- mercaptobenzoxazole (C of 7.12mg7H5NOS above-mentioned solution) is added, is stirred to react 15 minutes.Meanwhile at 1 hour
It is interior by 10.8mg NaBH4It is dissolved in acetonitrile.Then, above two solution is mixed in flask, and stirs and puts at 25 DEG C
It sets 3 hours.By rotary evaporation remove acetonitrile solvent, obtained solid is washed with ether, with remove unreacted mercaptan and
Possible disulfide by-products.Then product is extracted with dichloromethane, obtains [the Cu with precision architecture6(C7H4NOS)6]2-
(it is abbreviated as Cu6).It is tested by ultraviolet-visible spectrum (UV-Vis), obtained Cu cluster is Cu6, see Fig. 1.Take 15 milligrams
Cu6500 milligrams of ZrO are added2, it is placed in Ultrasound Instrument after 15 minutes, being stirred overnight makes its aging, with atom number after dry out solvent
Cu cluster for 6 is the loaded catalyst (Cu in activated centre6/ZrO2), wherein Cu content is 0.8%；Its infrared figure is shown in figure
2.Catalytic reaction condition are as follows: the temperature for being catalyzed reaction is 100~150 DEG C, and pressure is 1~4MPa；Reaction gas is CO2:H2:N2,
Middle H2:CO2=1~3, N2As internal standard, catalytic performance is shown in Fig. 3.
Catalytic reaction condition are as follows: the temperature of preferred catalytic reaction is 130 degree, pressure 2MPa；Reaction gas is CO2:H2:N2,
Wherein H2:CO2=3, N2As internal standard.Under this condition, 100 are put into the autoclave with polytetrafluoroethyllining lining
Milligram catalyst, carbon dioxide is under the catalytic action of catalyst by hydrogen reducing to organic matter, after reaction 10 hours, titanium dioxide
Efficiency of carbon con version 3.6%, wherein the selectivity of methanol is 36%, methyl formate 64%；
Embodiment 3:
Under constant stirring in by 11.9mg acetylacetone copper (Cu (C5H7O2)2) be added 7.2mL acetonitrile mixed in flask
10min.Then by the 2- mercaptobenzoxazole (C of 7.12mg7H5NOS above-mentioned solution) is added, is stirred to react 15 minutes.Meanwhile In
By 10.8mg NaBH in 1 hour4It is dissolved in acetonitrile.Then, above two solution is mixed in flask, and at 25 DEG C
Stirring is placed 3 hours.Acetonitrile solvent is removed by rotary evaporation, obtained solid is washed with ether, it is unreacted to remove
Mercaptan and possible disulfide by-products.Then product is extracted with dichloromethane, obtains [the Cu with precision architecture6
(C7H4NOS)6]2-(it is abbreviated as Cu6).It is tested by ultraviolet-visible spectrum (UV-Vis), obtained Cu cluster is Cu6, see
Fig. 1.Take 15 milligrams of Cu6500 milligrams of MgO are added, are placed in Ultrasound Instrument after 15 minutes, being stirred overnight makes its aging, dry out solvent
The Cu cluster for being afterwards 6 using atom number is the loaded catalyst (Cu in activated centre6/MgO).Wherein Cu content is 0.8%.
Catalytic reaction condition are as follows: the temperature for being catalyzed reaction is 100~150 DEG C, and pressure is 1~4MPa；Reaction gas is CO2:H2:N2, wherein
H2:CO2=1~3, N2As internal standard, catalytic performance is shown in Fig. 3.
Catalytic reaction condition are as follows: the temperature of preferred catalytic reaction is 130 degree, pressure 2MPa；Reaction gas is CO2:H2:N2,
Wherein H2:CO2=3, N2As internal standard.Under this condition, 100 are put into the autoclave with polytetrafluoroethyllining lining
Milligram catalyst, carbon dioxide is under the catalytic action of catalyst by hydrogen reducing to organic matter, after reaction 10 hours, titanium dioxide
Efficiency of carbon con version 2.7%, wherein the selectivity of methanol is 45%, methyl formate 55%；
Embodiment 4:
Under constant stirring in by 8.52mg copper nitrate (Cu (NO3)2) be added 7.2mL acetonitrile 10min is mixed in flask.
Then by the 2- mercaptobenzoxazole (C of 7.12mg7H5NOS above-mentioned solution) is added, is stirred to react 15 minutes.Meanwhile at 1 hour
It is interior by 10.8mg NaBH4It is dissolved in acetonitrile.Then, above two solution is mixed in flask, and stirs and puts at 25 DEG C
It sets 3 hours.By rotary evaporation remove acetonitrile solvent, obtained solid is washed with ether, with remove unreacted mercaptan and
Possible disulfide by-products.Then product is extracted with dichloromethane, obtains [the Cu with precision architecture6(C7H4NOS)6]2-
(it is abbreviated as Cu6).It is tested by ultraviolet-visible spectrum (UV-Vis), obtained Cu cluster is Cu6, see Fig. 1.Take 75 milligrams
Cu6500 milligrams of MgO are added, are placed in Ultrasound Instrument after 15 minutes, being stirred overnight makes its aging, with atom number after dry out solvent
Cu cluster for 6 is the loaded catalyst (Cu in activated centre6/ MgO), wherein Cu content is 4%.Its XPS spectrum figure is shown in figure
4.Catalytic reaction condition are as follows: the temperature for being catalyzed reaction is 110 DEG C, pressure 1.5MPa；Reaction gas is CO2:H2:N2, wherein H2:
CO2=1, N2As internal standard.
Embodiment 5:
Under constant stirring in by 11.9mg acetylacetone copper (Cu (C5H7O2)2) be added 7.2mL acetonitrile mixed in flask
10min.Then by the 2- mercaptobenzoxazole (C of 7.12mg7H5NOS above-mentioned solution) is added, is stirred to react 15 minutes.Meanwhile In
By 10.8mg NaBH in 1 hour4It is dissolved in acetonitrile.Then, above two solution is mixed in flask, and at 25 DEG C
Stirring is placed 3 hours.Acetonitrile solvent is removed by rotary evaporation, obtained solid is washed with ether, it is unreacted to remove
Mercaptan and possible disulfide by-products.Then product is extracted with dichloromethane, obtains [the Cu with precision architecture6
(C7H4NOS)6]2-(it is abbreviated as Cu6).It is tested by ultraviolet-visible spectrum (UV-Vis), obtained Cu cluster is Cu6, see
Fig. 1.Take 150 milligrams of Cu6500 milligrams of MgO are added, are placed in Ultrasound Instrument after 15 minutes, being stirred overnight makes its aging, dry out solvent
The Cu cluster for being afterwards 6 using atom number is the loaded catalyst (Cu in activated centre6/ MgO), wherein Cu content is 8%.Its
High resolution electron microscopy is shown in Fig. 5.Catalytic reaction condition are as follows: the temperature for being catalyzed reaction is 140 DEG C, pressure 3.5MPa；Reaction gas is
CO2:H2:N2, wherein H2:CO2=2, N2As internal standard.
Embodiment 6:
Under constant stirring in by 11.9mg acetylacetone copper (Cu (C5H7O2)2) be added 7.2mL acetonitrile mixed in flask
10min.Then by the 2- mercaptobenzoxazole (C of 7.12mg7H5NOS above-mentioned solution) is added, is stirred to react 15 minutes.Meanwhile In
By 10.8mg NaBH in 1 hour4It is dissolved in acetonitrile.Then, above two solution is mixed in flask, and at 25 DEG C
Stirring is placed 3 hours.Acetonitrile solvent is removed by rotary evaporation, obtained solid is washed with ether, it is unreacted to remove
Mercaptan and possible disulfide by-products.Then product is extracted with dichloromethane, obtains [the Cu with precision architecture6
(C7H4NOS)6]2-(it is abbreviated as Cu6).It is tested by ultraviolet-visible spectrum (UV-Vis), obtained Cu cluster is Cu6, see
Fig. 1.Take 38 milligrams of Cu6500 milligrams of SiO are added2, it is placed in Ultrasound Instrument after 15 minutes, being stirred overnight makes its aging, dry out solvent
The Cu cluster for being afterwards 6 using atom number is the loaded catalyst (Cu in activated centre6/SiO2) wherein Cu content be 2%.,
XANES spectrogram is shown in Fig. 6.Catalytic reaction condition are as follows: the temperature for being catalyzed reaction is 120 DEG C, pressure 4MPa；Reaction gas is CO2:H2:
N2, wherein H2:CO2=2, N2As internal standard.
Claims (9)
1. a kind of carried copper cluster, which is characterized in that the cluster is the Cu cluster that atom number is 6, quality
Content are as follows: 0.1wt%~10wt%.
2. a kind of carried copper cluster according to claim 1, it is characterised in that carrier is transition metal oxide.
3. a kind of preparation method of carried copper cluster, it the following steps are included:
Step 1 prepares the solution that mass fraction is 0.1%~0.5% mantoquita；
Step 2, the solution for preparing the sodium borohydride (NaBH4) that mass fraction is 0.1%~0.3%；
2- mercaptobenzoxazole (the C that quality is 0.6 times of mantoquita quality is added into the solution of step 1 for step 37H5NOS)；
Step 4, by solution obtained in step 3, be added in the solution of the sodium borohydride in step 2 (NaBH4), and at 25 DEG C
Lower stirring is placed 3 hours；
Step 5 will obtain mixture by rotary evaporation removing acetonitrile solvent in step 4, remaining solid is washed with ether, it
After product is extracted with dichloromethane, obtain [the Cu with precision architecture6(C7H4NOS)6]2-；The cluster is abbreviated as Cu6；
Step 6, by Cu obtained in step 56, a certain amount of oxide (MO) carrier is added, is placed in Ultrasound Instrument after 15 minutes,
Being stirred overnight makes its aging, and the Cu cluster for being 6 using atom number after dry out solvent is the loaded catalyst in activated centre
(Cu6/MO)。
4. a kind of preparation method of carried copper cluster according to claim 3, which is characterized in that described in step 1
Mantoquita be acetylacetone copper or copper nitrate.
5. a kind of preparation method of carried copper cluster according to claim 3, which is characterized in that described in step 2
Sodium borohydride solution be water, methanol, ethyl alcohol, isopropanol or butanol one kind.
6. a kind of preparation method of carried copper cluster according to claim 3 is it is characterized in that, described in step 5
Organic solvent is one of methylene chloride, toluene, acetone, acetonitrile, ether, dimethylformamide or tetrahydrofuran.
7. a kind of preparation method of carried copper cluster according to claim 3, which is characterized in that described in step 6
Oxide carrier be silica, aluminium oxide, magnesia, zirconium oxide, titanium oxide, molybdenum oxide, zinc oxide or cobalt oxide in
It is a kind of.
8. a kind of carried copper cluster is used to be catalyzed the application method of the catalyst of carbon dioxide hydrogenation reaction, feature exists
In the temperature for being catalyzed reaction is 100~150 degree, and pressure is 1~4MPa；Reaction gas is CO2、H2、N2。
9. a kind of carried copper cluster according to claim 8 is used to be catalyzed the catalyst of carbon dioxide hydrogenation reaction
Application method, which is characterized in that the temperature for being catalyzed reaction is 130 degree；The H2:CO2=1~3, N2As internal standard.
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| CN113769761A (en) * | 2021-09-22 | 2021-12-10 | 电子科技大学 | Preparation method and application of cadmium sulfide surface anchoring copper cluster |
| CN114588929A (en) * | 2022-03-16 | 2022-06-07 | 安徽大学 | Supported copper nanocluster catalyst and application thereof in AHA coupling reaction |
| CN115245824A (en) * | 2022-03-09 | 2022-10-28 | 南京大学 | Precise metal cluster-based composite catalyst and preparation method and application thereof |
| CN116371411A (en) * | 2023-02-08 | 2023-07-04 | 天津大学 | Copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier and application thereof |
| CN116371412A (en) * | 2023-02-20 | 2023-07-04 | 天津大学 | Method for regulating and controlling Cu atom cluster size in copper-based catalyst |
| CN116393135A (en) * | 2023-02-08 | 2023-07-07 | 天津大学 | Preparation method of copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier |
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| CN113769761A (en) * | 2021-09-22 | 2021-12-10 | 电子科技大学 | Preparation method and application of cadmium sulfide surface anchoring copper cluster |
| CN113769761B (en) * | 2021-09-22 | 2022-07-29 | 电子科技大学 | Preparation method and application of cadmium sulfide surface anchoring copper cluster |
| CN115245824A (en) * | 2022-03-09 | 2022-10-28 | 南京大学 | Precise metal cluster-based composite catalyst and preparation method and application thereof |
| CN114588929A (en) * | 2022-03-16 | 2022-06-07 | 安徽大学 | Supported copper nanocluster catalyst and application thereof in AHA coupling reaction |
| CN114588929B (en) * | 2022-03-16 | 2023-10-03 | 安徽大学 | Supported copper nanocluster catalyst and application thereof in AHA coupling reaction |
| CN116371411A (en) * | 2023-02-08 | 2023-07-04 | 天津大学 | Copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier and application thereof |
| CN116393135A (en) * | 2023-02-08 | 2023-07-07 | 天津大学 | Preparation method of copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier |
| CN116393135B (en) * | 2023-02-08 | 2024-09-27 | 天津大学 | Preparation method of copper-based catalyst loaded with Cu atom clusters or Cu single atoms by mixed carrier |
| CN116371412A (en) * | 2023-02-20 | 2023-07-04 | 天津大学 | Method for regulating and controlling Cu atom cluster size in copper-based catalyst |
| CN116371412B (en) * | 2023-02-20 | 2024-09-06 | 天津大学 | Method for regulating and controlling Cu atom cluster size in copper-based catalyst |
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