CN106378141B - ZnO/Cu nanocrystalline composite material and its preparation method and application - Google Patents
ZnO/Cu nanocrystalline composite material and its preparation method and application Download PDFInfo
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- CN106378141B CN106378141B CN201611001410.3A CN201611001410A CN106378141B CN 106378141 B CN106378141 B CN 106378141B CN 201611001410 A CN201611001410 A CN 201611001410A CN 106378141 B CN106378141 B CN 106378141B
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 23
- 229910001868 water Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002159 nanocrystal Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 72
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 57
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 12
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 239000008246 gaseous mixture Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 30
- 239000002707 nanocrystalline material Substances 0.000 abstract description 6
- 239000010949 copper Substances 0.000 description 119
- 238000006243 chemical reaction Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000011160 research Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of ZnO/Cu nanocrystalline composite material, ZnO is carried on Cu nanocrystal surface, and the ZnO/Cu nanocrystalline composite material is cube or octahedron.It is applied to water gas shift reation, compared with Cu is nanocrystalline, illustrate high catalytic performance facilitation, simultaneously for the ZnO/Cu nanocrystalline material of different-shape, also great catalytic performance difference is shown, the experimental results showed that cube ZnO/Cu has fabulous catalytic performance for water gas shift reation.
Description
Technical field
The present invention relates to technical face catalytic field more particularly to a kind of ZnO/Cu nanocrystalline composite material and its preparation sides
Method and application.
Background technique
Ni metal largely exists in nature as a kind of cheap material.Meanwhile the Cu conduct in catalytic field
A kind of metal material easily to appraise at the current rate, it may have be widely applied, industrially such as methanol-fueled CLC, water gas shift reation, methanol weight
Whole and Selective Oxidation etc. suffers from fabulous catalytic performance.Therefore, in chemistry, chemical industry and production of energy application
In all occupy high status.
Wherein, water gas shift reation is industrial production cleaning H2One of important reaction, data are shown, nearly 95%
H2The reforming reaction from substances such as coal, petroleum, natural gas, wood materials, debirs and biomass is generated, however,
The H obtained by reforming reaction2In contain 1%~10%CO, CO gas is serious has poisoned proton membrane fuel battery for these
Anode Pt electrode catalyst, and can be good at reducing by water gas shift reation and reform the content of CO in gas and therefore pass through
Water gas shift reation cleans H to be mass produced2It is highly desirable and very urgent, and it is extensive to have caused people
Research interest.In addition, (such as methanol closes for water gas shift reation and its reversible reaction and current many industrial catalysis techniques
At, the synthesis of methanol steam reforming, ammonia, coal gasification and catalyst combustion reaction) be also directly or indirectly associated.Currently,
Industrially there are two class commercial catalysts for water gas shift reation, one kind is superheated vapor transformation catalyst-ferrum-based catalyst；
Another kind of is low temperature water-gas shift-copper-based catalysts.Water gas shift reation is an exothermic reaction (Δ H=-41.1kJ/mol), because
This is from thermodynamics, the lower progress for being more advantageous to reaction of temperature, however, by dynamic (dynamical) influence, high temperature is more advantageous
In the quickening of reaction rate, therefore, the rate for selecting a kind of suitable catalyst to accelerate reaction in lower temperature is to Guan Chong
It wants.So research of the water gas shift reation based on copper-based catalysts is the research field of a unusual hot spot.
Up to the present, the micro catalytic for being used to study water gas shift reation despite the presence of a large amount of research work reacts machine
Reason, still, catalytic reaction mechanism and the active sites of catalysis reaction are always all without explicitly fixed in detailed copper-based catalysts
By.The study found that it has widely been considered as a kind of the anti-of structure sensitive property that copper-based catalysts, which are applied to water gas shift reation,
It answers, many research workers pass through the different Cu single-crystal surface of monocrystalline model catalysis system and theoretical research in steam
The catalytic mechanism of structure sensitive property and reaction in conversion reaction, however these researchs are all difficult in true catalysis reaction item
The structure sensitive property of Cu is really studied in part.Recently, with the development of nanometer synthetic technology, research workers can be manipulated
The single crystal face of synthesis exposure nanocrystalline material, these nano crystal materials can be very good to replace monocrystalline model catalyst,
Catalysis reaction test is carried out under true catalytic reaction condition as powder catalytic.However, since Ni metal itself compares
Vivaciously, thus the nanocrystalline material of its regular appearance is difficult to be synthesized.
And Cu nanocrystalline material causes since particle size is too big and there are problems that high-temperature catalytic stability
There is the problems such as active too low and high-temperature stability is insufficient in water gas shift reation in it.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of ZnO/Cu nanocrystalline composite material and its system
The composite material of Preparation Method and application, preparation is applied in water gas shift reation, catalytic performance with higher.
The present invention provides a kind of ZnO/Cu nanocrystalline composite material, ZnO is carried on Cu nanocrystal surface, the ZnO/Cu
Nanocrystalline composite material is cube or octahedron.
The present invention also provides a kind of preparation methods of above-mentioned ZnO/Cu nanocrystalline composite material, comprising the following steps:
A) Cu is provided2O is nanocrystalline, the Cu2O nanocrystalline is cube or octahedron；
B) using zinc nitrate as presoma, zinc nitrate is uniformly distributed in by Cu using the method for incipient impregnation2O is nanocrystalline
Surface roasts under an inert atmosphere, obtains ZnO/Cu2O nanocrystalline composite material；
C)ZnO/Cu2O nanocrystalline composite material roasts under reducing atmosphere, obtains ZnO/Cu nanocrystalline composite material；Institute
The pattern and the Cu in the step A) for stating ZnO/Cu nanocrystalline composite material2O is nanocrystalline consistent.
Preferably, the step A) specifically:
By CuCl2Aqueous solution is reacted with NaOH solution and ascorbic acid solution, obtains Cu2O is nanocrystalline, the Cu2O
Nanocrystalline is cube；
Or by CuCl2Aqueous solution is reacted with polyvinylpyrrolidone, NaOH solution and ascorbic acid solution, is obtained
Surface has the protectant Cu of polyvinylpyrrolidone2O is nanocrystalline；
Above-mentioned surface is had into the protectant Cu of polyvinylpyrrolidone2O is nanocrystalline, in C3H6/O2In/Ar mixed gas
It is roasted, obtains Cu2O is nanocrystalline, the Cu2O is nanocrystalline for octahedron.
Preferably, the step B) specifically:
By Cu2The nanocrystalline method using incipient impregnation of O impregnates zinc nitrate alcohol solution, the Cu2O is nanocrystalline and nitre
The mass volume ratio of sour zinc alcohol solution is 1mg:1 μ l, and the concentration of the zinc nitrate alcohol solution is (1.3 × 10-2~1.3)
Mol/L, the sample after dipping, is roasted for 300 DEG C~350 DEG C at inert gas Ar.
Preferably, the step C) in reducing atmosphere be CO, H2Or CO+H2O。
Preferably, the step C) specifically:
The ZnO/Cu that step B) is obtained2O nanocrystalline composite material roasts under reducing gas；
The reducing gas is 1%~10%CO/Ar gaseous mixture, as the ZnO/Cu2O nanocrystalline composite material is cube
When body, the maturing temperature is 125~225 DEG C, as the ZnO/Cu2When O nanocrystalline composite material is octahedra, the roasting
Temperature is 150~250 DEG C；
Or the reducing gas is 1%~10%H2/ Ar gaseous mixture, as the ZnO/Cu2O nanocrystalline composite material is
When cube, the maturing temperature is 100~200 DEG C, as the ZnO/Cu2It is described when O nanocrystalline composite material is octahedra
Maturing temperature is 125~225 DEG C；
Or the reducing gas is 1%~10%CO and 5%~15%H2O/Ar gaseous mixture, as the ZnO/Cu2O receives
When rice crystal composite material is cube, the maturing temperature is 125~225 DEG C, as the ZnO/Cu2O nanocrystalline composite material
When for octahedron, the maturing temperature is 150~250 DEG C.
The present invention also provides ZnO/Cu nanometers prepared by above-mentioned ZnO/Cu nanocrystalline composite material or above-mentioned preparation method
Application of the crystal composite material as water gas shift reation catalyst.
Compared with prior art, the present invention provides a kind of ZnO/Cu nanocrystalline composite material, it is nanocrystalline that ZnO is carried on Cu
Surface, the ZnO/Cu nanocrystalline composite material are cube or octahedron.It is applied to water gas shift reation, with Cu nanometers
Crystal phase ratio illustrates high catalytic performance facilitation, simultaneously for the ZnO/Cu nanocrystalline material of different-shape, also shows
Great catalytic performance difference is gone out, the experimental results showed that cube ZnO/Cu has preferably catalysis for water gas shift reation
Performance.
Detailed description of the invention
Fig. 1 is cube Cu2O nanocrystalline SEM figure；
Fig. 2 is octahedron Cu2O nanocrystalline SEM figure；
Fig. 3 is cube ZnO/Cu2The SEM of O nanocrystalline composite material schemes；
Fig. 4 is octahedron ZnO/Cu2The SEM of O nanocrystalline composite material schemes；
Fig. 5 is that the SEM of cube ZnO/Cu nanocrystalline composite material schemes；
Fig. 6 is that the SEM of octahedron ZnO/Cu nanocrystalline composite material schemes；
Fig. 7 is that synthesis obtains two kinds of cube, octahedron ZnO/Cu2The XRD diagram of O and ZnO/Cu nanocrystalline composite material；
Fig. 8 is cube, octahedra two kinds of ZnO/Cu nanocrystalline composite materials are applied to the work that water gas shift reation obtains
Property figure.
Specific embodiment
The present invention provides a kind of ZnO/Cu nanocrystalline composite material, ZnO is carried on Cu nanocrystal surface, the ZnO/Cu
Nanocrystalline composite material is cube or octahedron.
Above-mentioned ZnO/Cu nanocrystalline composite material is applied to water gas shift reation, has fabulous catalytic performance.It is received with Cu
Meter Jing Xiang ratio illustrates high catalytic performance facilitation, simultaneously for the ZnO/Cu nanocrystalline material of different-shape, also table
Great catalytic performance difference is revealed.
The present invention also provides the preparation methods of above-mentioned ZnO/Cu nanocrystalline composite material, comprising the following steps:
A) Cu is provided2O is nanocrystalline, the Cu2O nanocrystalline is cube or octahedron；
B) using zinc nitrate as presoma, zinc nitrate is uniformly distributed in by Cu using the method for incipient impregnation2O is nanocrystalline
Surface roasts under an inert atmosphere, obtains ZnO/Cu2O nanocrystalline composite material；
C)ZnO/Cu2O nanocrystalline composite material roasts under reducing atmosphere, obtains ZnO/Cu nanocrystalline composite material；Institute
The pattern and the Cu in the step A) for stating ZnO/Cu nanocrystalline composite material2O is nanocrystalline consistent.
The present invention is with cube or octahedron Cu2O nanocrystalline is raw material.
Above-mentioned cube Cu2O is nanocrystalline preferably to be prepared in accordance with the following methods for raw material:
By CuCl2Aqueous solution is reacted with NaOH solution and ascorbic acid solution, obtains Cu2O is nanocrystalline, the Cu2O
Nanocrystalline is cube.
The CuCl2The concentration of aqueous solution is preferably 0.005~0.02mol/l.The temperature of the reaction is preferably 45~
60 DEG C, the time of the reaction is preferably 3~8h.
The NaOH solution is NaOH aqueous solution, and concentration is preferably 1~3mol/l.The ascorbic acid solution is anti-bad
Hematic acid aqueous solution, concentration are preferably 0.5~0.8mol/l.
The CuCl2, NaOH and ascorbic acid molar ratio be preferably 1:(15~25): (4~8).
Above-mentioned octahedron Cu2O is nanocrystalline preferably to be prepared in accordance with the following methods for raw material:
By CuCl2Aqueous solution is reacted with polyvinylpyrrolidone (PVP), NaOH solution and ascorbic acid solution, is obtained
The protectant Cu of polyvinylpyrrolidone is had to surface2O is nanocrystalline；
The present invention is preferably first by CuCl2Aqueous solution is uniformly mixed with polyvinylpyrrolidone, then be added NaOH solution and
Ascorbic acid solution.
The CuCl2The concentration of aqueous solution is preferably 0.005~0.02mol/l.The temperature of the reaction is preferably 45~
60 DEG C, the time of the reaction is preferably 3~8h.
The NaOH solution is NaOH aqueous solution, and concentration is preferably 1~3mol/l.The ascorbic acid solution is anti-bad
Hematic acid aqueous solution, concentration are preferably 0.5~0.8mol/l.
The CuCl2, PVP, NaOH and ascorbic acid molar ratio be preferably 1:(0.1~0.5): (15~25): (4~
8)。
Then above-mentioned surface is had into the protectant Cu of polyvinylpyrrolidone2O is nanocrystalline, in C3H6/O2/ Ar gaseous mixture
It is roasted in body, obtains Cu2O is nanocrystalline, the Cu2O is nanocrystalline to be octahedra, and surface is clean, that is, is free of PVP protective agent.
The temperature of the roasting is preferably 150~250 DEG C, and the time of roasting is preferably 20~50min.The liter of the roasting
Warm speed is preferably 3~8 DEG C/min.
Then by the Cu of above-mentioned preparation2The nanocrystalline method using incipient impregnation of O impregnates zinc nitrate alcohol solution, at it
The ZnO of area load ZnO, surface have good facilitation for water gas shift reation.The Cu2O is nanocrystalline and nitric acid
The mass volume ratio of zinc alcohol solution is preferably 1mg:1 μ l, and the concentration of the zinc nitrate alcohol solution is preferably (1.3 × 10-2~
1.3) mol/L is roasted at inert atmosphere Ar, and maturing temperature is 300 DEG C~350 DEG C.
In some embodiments of the invention, the step B) specifically:
Take 200mg cube Cu2O is nanocrystalline to be placed in small crucible, use the mode of incipient impregnation impregnate volume for
200ul, concentration are (1.3 × 10-2~1.3) the zinc nitrate alcohol solution of mol/L after ultrasonic 30min, is placed in drier for 24 hours,
300~350 DEG C are risen to 1~5 DEG C/min heating rate in an inert atmosphere later, then constant temperature 2h is down to room temperature naturally, after
And obtain cube ZnO/Cu2O nanocrystalline composite material；
Or take 200mg octahedron Cu2O is nanocrystalline to be placed in small crucible, and volume is impregnated by the way of incipient impregnation
It is (1.3 × 10 for 200ul, concentration-2~1.3) the zinc nitrate alcohol solution of mol/L after ultrasonic 30min, is placed in drier
For 24 hours, 300~350 DEG C are risen to 1~5 DEG C/min heating rate in an inert atmosphere later, then constant temperature 2h is down to room naturally
Temperature then obtains octahedra ZnO/Cu2O nanocrystalline composite material.
Then to the ZnO/Cu2O nanocrystalline composite material is roasted under reducing atmosphere, carries out constant temperature reduction, institute
Stating reducing atmosphere is preferably CO, H2Or CO+H2The reducibility gas such as O.
In some embodiments of the invention, above-mentioned roasting specifically:
The ZnO/Cu that will be obtained2O nanocrystalline composite material roasts under reducing gas；
The reducing gas is 1%~10%CO/Ar gaseous mixture, as the ZnO/Cu2O nanocrystalline composite material is cube
When body, the maturing temperature is 125~225 DEG C, as the ZnO/Cu2When O nanocrystalline composite material is octahedra, the roasting
Temperature is 150~250 DEG C；
Or the reducing gas is 1%~10%H2/ Ar gaseous mixture, as the ZnO/Cu2O nanocrystalline composite material is
When cube, the maturing temperature is 100~200 DEG C, as the ZnO/Cu2It is described when O nanocrystalline composite material is octahedra
Maturing temperature is 125~225 DEG C；
Or the reducing gas is 1%~10%CO and 5%~15%H2O/Ar gaseous mixture, as the ZnO/Cu2O receives
When rice crystal composite material is cube, the maturing temperature is 125~225 DEG C, as the ZnO/Cu2O nanocrystalline composite material
When for octahedron, the maturing temperature is 150~250 DEG C.
The heating rate of above-mentioned roasting is preferably 1~5 DEG C/min.The time of the roasting is preferably 1~2h.
The roasting carries out preferably in tube furnace.
After roasting, it is cooled to room temperature, the ZnO/Cu nanocrystalline composite material of different-shape can be obtained.The ZnO/Cu receives
The pattern and its raw material Cu of rice crystal composite material2O nanocrystalline consistent appearance.
The method that the present invention uses incipient impregnation forms the ZnO/Cu that ZnO is carried on different-shape Cu nanocrystal surface
Nanocrystalline composite material, the ZnO on surface illustrate excellent catalysis reaction facilitation.
Provided by the invention preparation method is simple, does not need using special laboratory apparatus, reality that also need not be cumbersome
Step is tested, only a kind of experiment knot experimentally hardly resulted in need to can be obtained using experiment method simple in synthesis field
Fruit.It will be obvious from gained water gas shift reation catalytic activity test result, ZnO loads the Cu for different-shape
It is nanocrystalline all to promote performance with splendid water gas shift reation, and cube ZnO/Cu activity is best, has greatly guidance
Application function, while the high performance water gas shift reation catalyst of synthesizing new can also be designed on this basis.
The present invention also provides ZnO/Cu nanometers prepared by above-mentioned ZnO/Cu nanocrystalline composite material or above-mentioned preparation method
Application of the crystal composite material as water gas shift reation catalyst illustrates fabulous catalysis compared with corresponding Cu is nanocrystalline
Activity promoting.
In some embodiments of the invention, the application specifically: take ZnO/Cu nanocrystalline composite material 50~
150mg and water gas shift reation inert material Al2O350~100mg is placed in catalyst reaction device after evenly mixing, using solid
The CO+H of certainty ratio2O+Ar reaction gas, flow velocity are that 20~50ml/min is opened with 1~5 DEG C/min heating rate from 100 DEG C
Begin, a point is taken every 25 DEG C, after keeping the temperature 30~50min, using the gas component in on-line gas chromatography detection tail gas, and
The conversion ratio of catalysis reaction is calculated by the reduction amount of wherein CO.
Above-mentioned on-line gas chromatography preferably uses good fortune to found 9790 gas chromatographs, 5A molecular sieve chromatography column, and High Purity Hydrogen is made
For carrier gas.
Catalytic activity conclusion for the ZnO/Cu nanocrystalline composite material of different-shape, in water gas shift reation
Are as follows: 1. it is nanocrystalline to be respectively higher than its corresponding Cu for the catalytic performance of water gas shift reation by the ZnO/Cu of two kinds of different-shapes
Catalytic performance, it was demonstrated that the addition of ZnO promotes the nanocrystalline catalytic performance in water gas shift reation of Cu；2. ZnO load
Catalytic performance of the cube Cu nanocrystalline (cube ZnO/Cu) in water-gas shift is higher than octahedra Cu nanometers of ZnO load
The catalytic performance of brilliant (octahedra ZnO/Cu).
It can be evident that from obtained experimental result, be closed using the methods of topological reduction method, incipient impregnation
At the ZnO/Cu nanocrystalline composite material of different-shape is obtained, the nanocrystalline catalysis reactivity of original Cu can greatly be improved
Can, there is fabulous application prospect.
In order to further illustrate the present invention, below with reference to embodiment to ZnO/Cu nanocrystalline composite material provided by the invention
And its preparation method and application be described in detail.
Embodiment 1
Cube Cu2O nanocrystalline synthesis
The CuCl of 100ml0.01mol/l is taken with 250ml three-necked flask2Aqueous solution is placed in oil bath pan, in 55 DEG C of oil baths
Constant temperature 30min sequentially adds 10ml 2mol/lNaOH solution and 10ml 0.6mol/l ascorbic acid solution later, reacts 5h.
Last centrifuge washing, vacuum drying 12h, then obtain cube Cu2O is nanocrystalline.
Its pattern is detected, sees that Fig. 1, Fig. 1 are cube Cu2O nanocrystalline SEM figure.
Embodiment 2
Octahedra Cu2O nanocrystalline synthesis
The CuCl of 100ml 0.01mol/l is taken with 250ml three-necked flask2Aqueous solution is placed in oil bath pan, is then added
4.44g PVP(Mw=30000), the constant temperature 30min in 55 DEG C of oil baths, sequentially add later 10ml 2mol/l NaOH solution and
10ml 0.6mol/l ascorbic acid solution reacts 3h.Last centrifuge washing, vacuum drying 12h, then obtain surface with PVP
Protectant octahedron Cu2O is nanocrystalline.Later, take the surface 150mg with the protectant octahedron Cu of PVP2O sample is placed in tubular type
In furnace, using the C of fixed proportion3H6/O2/ Ar mixed gas is 20ml/min by sample with flow velocity, heating rate is 5 DEG C/
Min rises to 200 DEG C from room temperature, later constant temperature 30min, then is down to room temperature naturally, then obtains the clean octahedra Cu in surface2O
It is nanocrystalline.
Its pattern is detected, sees that Fig. 2, Fig. 2 are octahedra Cu2O nanocrystalline SEM figure.
Embodiment 3
Cube ZnO/Cu2The synthesis of O nanocrystalline composite material
The cube Cu for taking above-mentioned synthesis to obtain2The nanocrystalline 200mg of O is placed in small crucible, while preparing a certain concentration
The zinc nitrate alcohol solution of 0.13mol/L takes 200 μ l incipient impregnations in cube Cu2It is ultrasonic later on O is nanocrystalline
30min, room temperature, which is stood, in drier places for 24 hours, obtained dried powder is placed in tube furnace, under an inert atmosphere
350 DEG C of roasting 2h, heating rate are 2 DEG C/min, are finally down to room temperature naturally, then obtain cube ZnO/Cu2O is nanocrystalline multiple
Condensation material.
It is above-mentioned to prepare cube ZnO/Cu2The reagent used during O nanocrystalline composite material has zinc nitrate, dehydrated alcohol
And the experimental articles such as ultrapure water, gained is bought by market
Its pattern is detected, sees that Fig. 3, Fig. 3 are cube ZnO/Cu2O nanocrystalline SEM figure.
To the ZnO/Cu of preparation2As a result the nanocrystalline progress single crystal diffraction analysis of O is shown in that Fig. 7, Fig. 7 are prepared by the present invention vertical
Two kinds of cube, octahedron ZnO/Cu2The XRD diagram of O and ZnO/Cu nanocrystalline composite material.
Embodiment 4
Octahedra ZnO/Cu2The synthesis of O nanocrystalline composite material
Take the octahedra Cu that above-mentioned synthesis obtains2The nanocrystalline 200mg of O is placed in small crucible, while preparing a certain concentration
The zinc nitrate alcohol solution of 0.13mol/L takes 200 μ l incipient impregnations in octahedra Cu2It is ultrasonic later on O is nanocrystalline
30min, room temperature, which is stood, in drier places for 24 hours, obtained dried powder is placed in tube furnace, under an inert atmosphere
350 DEG C of roasting 2h, heating rate are 2 DEG C/min, are finally down to room temperature naturally, then obtain octahedra ZnO/Cu2O is nanocrystalline multiple
Condensation material.
Above-mentioned preparation octahedron ZnO/Cu2The reagent used during O nanocrystalline composite material has zinc nitrate, dehydrated alcohol
And the experimental articles such as ultrapure water buy gained by market
Its pattern is detected, sees that Fig. 4, Fig. 4 are octahedra ZnO/Cu2O nanocrystalline SEM figure.
To the ZnO/Cu of preparation2As a result the nanocrystalline progress single crystal diffraction analysis of O is shown in that Fig. 7, Fig. 7 are prepared by the present invention vertical
Two kinds of cube, octahedron ZnO/Cu2The XRD diagram of O and ZnO/Cu nanocrystalline composite material.
Embodiment 5
Cube ZnO/Cu nanocrystalline composite material synthesis and its in steam reacting condition catalytic activity test
The cube ZnO/Cu for taking above-mentioned synthesis to obtain2O nanocrystalline composite material 100mg is placed in tube furnace, using 5%
CO/Ar mixed gas rises to 200 DEG C by sample, then with the heating rate of 1 DEG C/min with the gas flow rate of 30ml/min, later
Constant temperature 1h, then it is down to room temperature naturally, then obtain cube ZnO/Cu nanocrystalline composite material, the cube that will finally obtain
ZnO/Cu is placed in a vacuum drying oven preservation.
Its pattern is detected, sees that Fig. 5, Fig. 5 are the nanocrystalline SEM figures of cube ZnO/Cu.
Progress single crystal diffraction analysis nanocrystalline to the ZnO/Cu of preparation, is as a result shown in that Fig. 7, Fig. 7 are prepared by the present invention cube
Two kinds of body, octahedron ZnO/Cu2The XRD diagram of O and ZnO/Cu nanocrystalline composite material.
It is the related catalytic performance test done to the obtained catalyst of the present embodiment below:
The cube ZnO/Cu nanocrystalline composite material 50mg and water gas shift reation inert carrier Al obtained2O3 50mg
Uniformly mixing, the group of reaction gas are divided into 4.5%CO+10%H2O+85.5%Ar, reaction flow velocity are 30ml/min, heating rate
A point is adopted every 25 DEG C, (good fortune founds 9790 gas phase colors by on-line gas chromatography for 1 DEG C/min, each point heat preservation 50min
Spectrometer, chromatographic column are 5A molecular sieve, carrier gas H2) gas composition in detection gas component, and counted by the reduction amount of CO
Calculate the conversion ratio of reaction.
The active figure that the ZnO/Cu nanocrystalline composite material is applied to water gas shift reation is shown in Fig. 8.Experimental result discovery
Which show splendid catalytic performances.
Embodiment 6
Octahedra ZnO/Cu nanocrystalline composite material synthesis and its in steam reacting condition catalytic activity test
Take the octahedra ZnO/Cu that above-mentioned synthesis obtains2O nanocrystalline composite material 100mg is placed in tube furnace, using 5%
CO/Ar mixed gas rises to 200 DEG C by sample, then with the heating rate of 1 DEG C/min with the gas flow rate of 30ml/min, herein
Constant temperature 1h, is down to room temperature naturally later, then obtains octahedra ZnO/Cu nanocrystalline composite material, the octahedron that will finally obtain
ZnO/Cu is placed in a vacuum drying oven preservation.
Its pattern is detected, sees that Fig. 6, Fig. 6 are the nanocrystalline SEM figures of octahedra ZnO/Cu.
Progress single crystal diffraction analysis nanocrystalline to the ZnO/Cu of preparation, is as a result shown in that Fig. 7, Fig. 7 are prepared by the present invention cube
Two kinds of body, octahedron ZnO/Cu2The XRD diagram of O and ZnO/Cu nanocrystalline composite material.
It is the related catalytic performance test done to catalyst obtained by the present embodiment below:
The octahedra ZnO/Cu nanocrystalline composite material 50mg and water gas shift reation inert carrier Al obtained2O3 50mg
Uniformly mixing, the group of reaction gas are divided into 4.5%CO+10%H2O+85.5%Ar, reaction flow velocity are 30ml/min, heating rate
A point is adopted every 25 DEG C, (good fortune founds 9790 gas phase colors by on-line gas chromatography for 1 DEG C/min, each point heat preservation 50min
Spectrometer, chromatographic column are 5A molecular sieve, carrier gas H2) gas composition in detection gas component, and counted by the reduction amount of CO
Calculate the conversion ratio of reaction.
The active figure that the ZnO/Cu nanocrystalline composite material is applied to water gas shift reation is shown in Fig. 8.Experimental result discovery
Which show splendid catalytic performances.
Following reaction occurs for detection of the present invention:
Cu2O+CO→Cu+CO2
Cu2O+H2→Cu+H2O
CO+H2O→CO2+H2
The gas (carbon monoxide, argon gas, propylene and oxygen etc.) used in example 2~6 is bought from market.
Comparative example 1
Respectively with cube Cu, octahedron Cu50mg and water gas shift reation inert carrier Al2O350mg is uniformly mixed, instead
The group of gas is answered to be divided into 4.5%CO+10%H2O+85.5%Ar, reaction flow velocity are 30ml/min, and heating rate is 1 DEG C/min,
Each point heat preservation 50min, a point is adopted every 25 DEG C, (good fortune founds 9790 gas chromatographs, chromatographic column by on-line gas chromatography
For 5A molecular sieve, carrier gas H2) gas composition in detection gas component, and calculate by the reduction amount of CO the conversion of reaction
Rate.
Its active figure for being applied to water gas shift reation is shown in Fig. 8.
By above-described embodiment and comparative example it is found that ZnO/Cu nanocrystalline composite material prepared by the present invention becomes steam
Reaction is changed to have excellent catalytic properties.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (7)
1. a kind of ZnO/Cu nanocrystalline composite material, which is characterized in that ZnO is carried on Cu nanocrystal surface, and the ZnO/Cu receives
Rice crystal composite material is cube or octahedron.
2. the preparation method of ZnO/Cu nanocrystalline composite material described in claim 1, which comprises the following steps:
A) Cu is provided2O is nanocrystalline, the Cu2O nanocrystalline is cube or octahedron；
B) using zinc nitrate as presoma, zinc nitrate is uniformly distributed in by Cu using the method for incipient impregnation2O nanocrystal surface,
It roasts under an inert atmosphere, obtains ZnO/Cu2O nanocrystalline composite material；
C)ZnO/Cu2O nanocrystalline composite material roasts under reducing atmosphere, obtains ZnO/Cu nanocrystalline composite material；The ZnO/
The pattern of Cu nanocrystalline composite material and the Cu in the step A)2O is nanocrystalline consistent.
3. preparation method according to claim 2, which is characterized in that the step A) specifically:
By CuCl2Aqueous solution is reacted with NaOH solution and ascorbic acid solution, obtains Cu2O is nanocrystalline, the Cu2O nanometers
Crystalline substance is cube；
Or by CuCl2Aqueous solution is reacted with polyvinylpyrrolidone, NaOH solution and ascorbic acid solution, obtains surface
With the protectant Cu of polyvinylpyrrolidone2O is nanocrystalline；
Above-mentioned surface is had into the protectant Cu of polyvinylpyrrolidone2O is nanocrystalline, in C3H6/O2It is roasted in/Ar mixed gas
It burns, obtains Cu2O is nanocrystalline, the Cu2O is nanocrystalline for octahedron.
4. preparation method according to claim 2, which is characterized in that the step B) specifically:
By Cu2The nanocrystalline method using incipient impregnation of O impregnates zinc nitrate alcohol solution, the Cu2O is nanocrystalline and zinc nitrate
The mass volume ratio of alcohol solution is 1mg:1 μ l, and the concentration of the zinc nitrate alcohol solution is (1.3 × 10-2~1.3) mol/L,
Sample after dipping is roasted for 300 DEG C~350 DEG C at inert gas Ar.
5. preparation method according to claim 2, which is characterized in that the step C) in reducing atmosphere be CO, H2Or CO
+H2O。
6. preparation method according to claim 5, which is characterized in that the step C) specifically:
The ZnO/Cu that step B) is obtained2O nanocrystalline composite material roasts under reducing gas；
The reducing gas is 1%~10%CO/Ar gaseous mixture, as the ZnO/Cu2When O nanocrystalline composite material is cube,
The maturing temperature is 125~225 DEG C, as the ZnO/Cu2When O nanocrystalline composite material is octahedra, the maturing temperature
It is 150~250 DEG C；
Or the reducing gas is 1%~10%H2/ Ar gaseous mixture, as the ZnO/Cu2O nanocrystalline composite material is cube
When body, the maturing temperature is 100~200 DEG C, as the ZnO/Cu2When O nanocrystalline composite material is octahedra, the roasting
Temperature is 125~225 DEG C；
Or the reducing gas is 1%~10%CO and 5%~15%H2O/Ar gaseous mixture, as the ZnO/Cu2O is nanocrystalline
When composite material is cube, the maturing temperature is 125~225 DEG C, as the ZnO/Cu2O nanocrystalline composite material is eight
When the body of face, the maturing temperature is 150~250 DEG C.
7. ZnO/Cu nanocrystalline composite material described in claim 1 or the described in any item preparation method systems of claim 2~6
Application of the standby ZnO/Cu nanocrystalline composite material as water gas shift reation catalyst.
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| CN109745988B (en) * | 2017-11-08 | 2022-03-01 | 中国石油天然气股份有限公司 | Preparation method of Cu-based water gas shift reaction catalyst |
| CN109126800B (en) * | 2018-07-20 | 2020-11-06 | 西安交通大学 | Preparation method of cuprous oxide-copper-zinc oxide composite photocatalyst |
| US11339487B2 (en) | 2019-02-28 | 2022-05-24 | Honda Motor Co., Ltd. | Synergistic effects of multi-faceted CU2O nanocrystals for electrochemical CO2 reduction |
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