CN106378141A - ZnO/Cu nanometer crystal composite material, and preparation method and application thereof - Google Patents
ZnO/Cu nanometer crystal composite material, and preparation method and application thereof Download PDFInfo
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- CN106378141A CN106378141A CN201611001410.3A CN201611001410A CN106378141A CN 106378141 A CN106378141 A CN 106378141A CN 201611001410 A CN201611001410 A CN 201611001410A CN 106378141 A CN106378141 A CN 106378141A
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- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 239000013078 crystal Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 30
- 229910001868 water Inorganic materials 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims description 74
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 51
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 51
- 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229960005070 ascorbic acid Drugs 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
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000008246 gaseous mixture Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002159 nanocrystal Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 150000002835 noble gases Chemical class 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 238000006555 catalytic reaction Methods 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 238000002474 experimental method Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 124
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 238000011160 research Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002707 nanocrystalline material Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 241000282693 Cercopithecidae Species 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 4
- 238000009413 insulation 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
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005516 engineering process 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
- 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 230000008859 change Effects 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
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process 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
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process 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
- 230000009467 reduction 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
- 239000000126 substance 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 invention provides a ZnO/Cu nanometer crystal composite material. ZnO is loaded on the surface of Cu nanometer crystals; the ZnO/Cu nanometer crystal composite material is of a cube or octahedron structure. When the ZnO/Cu nanometer crystal composite material is applied to water gas conversion reaction, compared with the Cu nanometer crystals, the ZnO/Cu nanometer crystal composite material has the advantages that the high catalysis performance promoting effect is shown; meanwhile, for ZnO/Cu nanometer crystal materials with different appearances, great catalytic performance differences are also shown. Experiments show that the cube ZnO/Cu has good catalytic performance on the water gas conversion reaction.
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 side
Method and application.
Background technology
Ni metal as a kind of cheap material, substantial amounts of presence in nature.Meanwhile, Cu conduct in catalytic field
A kind of metal material easily appraising at the current rate, it may have be widely applied, industrially as methanol-fueled CLC, water gas shift reation, methanol weight
Whole and Selective Oxidation etc., suffers from fabulous catalytic performance.Therefore, it is in chemistry, chemical industry and production of energy application
In all occupy high status.
Wherein, water gas shift reation is that industrial production cleans H2One of important reaction, data display, nearly 95%
H2Produce the reforming reaction from materials such as coal, oil, natural gas, wood materials, debirs and biomass, however,
The H being obtained by reforming reaction2In contain 1%～10%CO, what these CO gases were serious has poisoned proton membrane fuel battery
Anode Pt electrode catalyst, and by water gas shift reation can be good at reduce reformation gas in CO content, therefore, pass through
Water gas shift reation carrys out large-scale production cleaning H2It is highly desirable to and very urgent, and it is extensive to have caused people
Research interest.Additionally, water gas shift reation and its reversible reaction and currently many industrial catalysis techniques are (as methanol closes
One-tenth, methanol steam reforming, ammonia synthesis, coal gasification and catalyst combustion reaction) also directly or indirectly it is associated.At present,
Industrially there are two class commercial catalysts for water gas shift reation, a class 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
, from thermodynamics, relatively low the carrying out being more beneficial for reacting of temperature, however, by dynamic (dynamical) impact, high temperature is more favourable for this
In the quickening of reaction rate, therefore, the speed that a kind of suitable catalyst accelerates reaction in relatively low temperature is selected to be heavy to closing
Want.So, water gas shift reation is based on the research field that the research of copper-based catalysts is a unusual focus.
Up to the present, it is used for studying the micro catalytic reaction machine of water gas shift reation despite the presence of substantial amounts of research work
Reason, but, in its detailed copper-based catalysts, the active sites of catalytic reaction mechanism and catalytic reaction are not all clearly fixed always
By.Research finds, it has been considered as widely a kind of the anti-of structure sensitive property that copper-based catalysts are applied to water gas shift reation
Should, many research workers pass through the different Cu single-crystal surface of monocrystalline model catalysis system and theoretical research in steam
Structure sensitive property in transformationreation and the catalytic mechanism of reaction, but these researchs are all difficult in real catalytic reaction bar
The true structure sensitive property studying Cu in part.Recently, with the development of nanometer synthetic technology, research workers can manipulate
Synthesis expose single crystal face nanocrystalline material, these nano crystal materials can be very good replace monocrystalline model catalyst,
Carry out catalytic reaction test under real catalytic reaction condition as powder catalytic.However, because Ni metal compares in itself
Vivaciously, thus the nanocrystalline material of its regular appearance is difficult to be synthesized.
And Cu nanocrystalline material, because particle size is too big and there is high-temperature catalytic stability, cause
It haves such problems as that in water gas shift reation activity is too low and high-temperature stability is not enough.
Content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of ZnO/Cu nanocrystalline composite material and its system
Preparation Method and application, the composite of preparation is applied in water gas shift reation, has higher catalytic performance.
The invention provides a kind of ZnO/Cu nanocrystalline composite material, ZnO is carried on Cu nanocrystal surface, described ZnO/Cu
Nanocrystalline composite material is cube or octahedron.
Present invention also offers a kind of preparation method of above-mentioned ZnO/Cu nanocrystalline composite material, comprise the following steps：
A) provide Cu2O is nanocrystalline, described Cu2O nanocrystalline for cube or octahedron；
B) using zinc nitrate as presoma, zinc nitrate is uniformly distributed in Cu by the method using incipient impregnation2O is nanocrystalline
Surface, roasting under an inert atmosphere, obtain ZnO/Cu2O nanocrystalline composite material；
C)ZnO/Cu2The roasting under reducing atmosphere of O nanocrystalline composite material, obtains ZnO/Cu nanocrystalline composite material；Institute
State the pattern of ZnO/Cu nanocrystalline composite material and described step A) in Cu2O is nanocrystalline consistent.
Preferably, described step A) it is specially：
By CuCl2Aqueous solution is reacted with NaOH solution and ascorbic acid solution, obtains Cu2O is nanocrystalline, described Cu2O
Nanocrystalline for cube；
Or by CuCl2Aqueous solution is reacted with Polyvinylpyrrolidone, NaOH solution and ascorbic acid solution, obtains
Surface carries the protectant Cu of Polyvinylpyrrolidone2O is nanocrystalline；
Above-mentioned surface is carried the protectant Cu of Polyvinylpyrrolidone2O is nanocrystalline, in C3H6/O2In/Ar mixed gas
Carry out roasting, obtain Cu2O is nanocrystalline, described Cu2O nanocrystalline for octahedron.
Preferably, described step B) it is specially：
By Cu2The method dipping zinc nitrate alcohol-water solution of O nanocrystalline employing incipient impregnation, described Cu2O is nanocrystalline and nitre
The mass volume ratio of sour zinc alcohol-water solution is 1mg：1 μ l, the concentration of described zinc nitrate alcohol-water solution is (1.3 × 10-2～1.3)
Mol/L, the sample after dipping, under noble gases Ar, 300 DEG C～350 DEG C carry out roasting.
Preferably, described step C) in reducing atmosphere be CO, H2Or CO+H2O.
Preferably, described step C) it is specially：
By step B) ZnO/Cu that obtains2The roasting under reducing gas of O nanocrystalline composite material；
Described reducing gas is 1%～10%CO/Ar gaseous mixture, as described ZnO/Cu2O nanocrystalline composite material be cube
During body, described sintering temperature is 125～225 DEG C, as described ZnO/Cu2When O nanocrystalline composite material is octahedra, described roasting
Temperature is 150～250 DEG C；
Or described reducing gas is 1%～10%H2/ Ar gaseous mixture, as described ZnO/Cu2O nanocrystalline composite material is
During cube, described sintering temperature is 100～200 DEG C, as described ZnO/Cu2When O nanocrystalline composite material is octahedra, described
Sintering temperature is 125～225 DEG C；
Or described reducing gas is 1%～10%CO and 5%～15%H2O/Ar gaseous mixture, as described ZnO/Cu2O receives
When rice crystal composite material is cube, described sintering temperature is 125～225 DEG C, as described ZnO/Cu2O nanocrystalline composite material
During for octahedron, described sintering temperature is 150～250 DEG C.
Present invention also offers the ZnO/Cu nanometer of above-mentioned ZnO/Cu nanocrystalline composite material or the preparation of above-mentioned preparation method
Crystal composite material is as the application of water gas shift reation catalyst.
Compared with prior art, the invention provides a kind of ZnO/Cu nanocrystalline composite material, it is nanocrystalline that ZnO is carried on Cu
Surface, described ZnO/Cu nanocrystalline composite material is cube or octahedron.It is applied to water gas shift reation, with Cu nanometer
Crystalline phase ratio, illustrates high catalytic performance facilitation, simultaneously for the ZnO/Cu nanocrystalline material of different-shape, also shows
Go out great catalytic performance difference, test result indicate that cube ZnO/Cu has more preferable catalysis for water gas shift reation
Performance.
Brief description
Fig. 1 is cube Cu2The nanocrystalline SEM figure of O；
Fig. 2 is octahedra Cu2The nanocrystalline SEM figure of O；
Fig. 3 is cube ZnO/Cu2The SEM figure of O nanocrystalline composite material；
Fig. 4 is octahedra ZnO/Cu2The SEM figure of O nanocrystalline composite material；
Fig. 5 is the SEM figure of cube ZnO/Cu nanocrystalline composite material；
Fig. 6 is the SEM figure of octahedra ZnO/Cu nanocrystalline composite material；
Fig. 7 obtains cube, octahedra two kinds of ZnO/Cu for synthesis2The XRD figure 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 invention provides a kind of ZnO/Cu nanocrystalline composite material, ZnO is carried on Cu nanocrystal surface, described 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.Receive with Cu
Meter Jing Xiang ratio, illustrates high catalytic performance facilitation, simultaneously for the ZnO/Cu nanocrystalline material of different-shape, also table
Reveal great catalytic performance difference.
Present invention also offers the preparation method of above-mentioned ZnO/Cu nanocrystalline composite material, comprise the following steps：
A) provide Cu2O is nanocrystalline, described Cu2O nanocrystalline for cube or octahedron；
B) using zinc nitrate as presoma, zinc nitrate is uniformly distributed in Cu by the method using incipient impregnation2O is nanocrystalline
Surface, roasting under an inert atmosphere, obtain ZnO/Cu2O nanocrystalline composite material；
C)ZnO/Cu2The roasting under reducing atmosphere of O nanocrystalline composite material, obtains ZnO/Cu nanocrystalline composite material；Institute
State the pattern of ZnO/Cu nanocrystalline composite material and described step A) in Cu2O is nanocrystalline consistent.
The present invention is with cube or octahedra Cu2O nanocrystalline for 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, described Cu2O
Nanocrystalline for cube.
Described CuCl2The concentration of aqueous solution is preferably 0.005～0.02mol/l.The temperature of described reaction be preferably 45～
60 DEG C, the time of described reaction is preferably 3～8h.
Described NaOH solution is NaOH aqueous solution, and its concentration is preferably 1～3mol/l.Described ascorbic acid solution is anti-bad
Hematic acid aqueous solution, its concentration is preferably 0.5～0.8mol/l.
Described CuCl2, the mol ratio of NaOH and ascorbic acid 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, obtains
Carry the protectant Cu of Polyvinylpyrrolidone to surface2O is nanocrystalline；
The present invention is preferably first by CuCl2Aqueous solution is mixed homogeneously with Polyvinylpyrrolidone, be subsequently adding NaOH solution and
Ascorbic acid solution.
Described CuCl2The concentration of aqueous solution is preferably 0.005～0.02mol/l.The temperature of described reaction be preferably 45～
60 DEG C, the time of described reaction is preferably 3～8h.
Described NaOH solution is NaOH aqueous solution, and its concentration is preferably 1～3mol/l.Described ascorbic acid solution is anti-bad
Hematic acid aqueous solution, its concentration is preferably 0.5～0.8mol/l.
Described CuCl2, the mol ratio of PVP, NaOH and ascorbic acid be preferably 1：(0.1～0.5)：(15～25)：(4～
8).
Then above-mentioned surface is carried the protectant Cu of Polyvinylpyrrolidone2O is nanocrystalline, in C3H6/O2/ Ar gaseous mixture
Carry out roasting in body, obtain Cu2O is nanocrystalline, described Cu2O nanocrystalline for octahedron, and surface is clean, that is, do not contain PVP protective agent.
The temperature of described roasting is preferably 150～250 DEG C, and the time of roasting is preferably 20～50min.The liter of described roasting
Warm speed is preferably 3～8 DEG C/min.
Then by the Cu of above-mentioned preparation2The method dipping zinc nitrate alcohol-water solution of O nanocrystalline employing incipient impregnation, at it
Area load ZnO, the ZnO on surface has good facilitation for water gas shift reation.Described Cu2O is nanocrystalline and nitric acid
The mass volume ratio of zinc alcohol-water solution is preferably 1mg：1 μ l, the concentration of described zinc nitrate alcohol-water solution is preferably (1.3 × 10-2~
1.3) mol/L, roasting under inert atmosphere Ar, sintering temperature is 300 DEG C～350 DEG C.
In some embodiments of the invention, described step B) it is specially：
Take 200mg cube Cu2O is nanocrystalline to be placed in monkey, and impregnating volume by the way of incipient impregnation is
200ul, concentration are (1.3 × 10-2～1.3) the zinc nitrate alcohol-water solution of mol/L, after ultrasonic 30min, is placed on 24h in exsiccator,
Rise to 300～350 DEG C with 1～5 DEG C/min heating rate in an inert atmosphere afterwards, constant temperature 2h, is then naturally down to room temperature, continues
And obtain cube ZnO/Cu2O nanocrystalline composite material；
Or take 200mg octahedron Cu2O is nanocrystalline to be placed in monkey, impregnates volume by the way of incipient impregnation
It is (1.3 × 10 for 200ul, concentration-2～1.3) the zinc nitrate alcohol-water solution of mol/L, after ultrasonic 30min, is placed in exsiccator
24h, rises to 300～350 DEG C with 1～5 DEG C/min heating rate afterwards in an inert atmosphere, and then constant temperature 2h is down to room naturally
Temperature, obtains octahedra ZnO/Cu then2O nanocrystalline composite material.
Then to described ZnO/Cu2O nanocrystalline composite material carries out roasting under reducing atmosphere, carries out constant temperature reduction, institute
State reducing atmosphere and be preferably CO, H2Or CO+H2The reducibility gas such as O.
In some embodiments of the invention, above-mentioned roasting is specially：
By the ZnO/Cu obtaining2The roasting under reducing gas of O nanocrystalline composite material；
Described reducing gas is 1%～10%CO/Ar gaseous mixture, as described ZnO/Cu2O nanocrystalline composite material be cube
During body, described sintering temperature is 125～225 DEG C, as described ZnO/Cu2When O nanocrystalline composite material is octahedra, described roasting
Temperature is 150～250 DEG C；
Or described reducing gas is 1%～10%H2/ Ar gaseous mixture, as described ZnO/Cu2O nanocrystalline composite material is
During cube, described sintering temperature is 100～200 DEG C, as described ZnO/Cu2When O nanocrystalline composite material is octahedra, described
Sintering temperature is 125～225 DEG C；
Or described reducing gas is 1%～10%CO and 5%～15%H2O/Ar gaseous mixture, as described ZnO/Cu2O receives
When rice crystal composite material is cube, described sintering temperature is 125～225 DEG C, as described ZnO/Cu2O nanocrystalline composite material
During for octahedron, described sintering temperature is 150～250 DEG C.
The programming rate of above-mentioned roasting is preferably 1～5 DEG C/min.The time of described roasting is preferably 1～2h.
Described roasting is carried out preferably in tube furnace.
After roasting, it is cooled to room temperature, you can obtain the ZnO/Cu nanocrystalline composite material of different-shape.Described ZnO/Cu receives
The pattern of rice crystal composite material and its raw material Cu2The nanocrystalline consistent appearance of O.
The method that the present invention adopts incipient impregnation, forms the ZnO/Cu that ZnO is carried on different-shape Cu nanocrystal surface
Nanocrystalline composite material, the ZnO on surface illustrates excellent catalytic reaction facilitation.
The preparation method that the present invention provides simple it is not necessary to using special experimental apparatus, reality that also need not be loaded down with trivial details
Test step, only need to can get a kind of experiment experimentally hardly resulting in knot using experiment method simple in synthesis field
Really.Will be obvious from gained water gas shift reation catalysis activity test result, ZnO loads the Cu for different-shape
Nanocrystalline all have splendid water gas shift reation promotion performance, and cube ZnO/Cu activity is optimal, has great guidance
Application function, also can design synthesizing new high performance water gas shift reation catalyst simultaneously on this basis.
Present invention also offers the ZnO/Cu nanometer of above-mentioned ZnO/Cu nanocrystalline composite material or the preparation of above-mentioned preparation method
Crystal composite material as the application of water gas shift reation catalyst, nanocrystalline with corresponding Cu compared with, illustrate fabulous catalysis
Activity promoting.
In some embodiments of the invention, described application is specially：Take ZnO/Cu nanocrystalline composite material 50～
150mg and water gas shift reation inert material Al2O350～100mg is placed in catalyst reaction device after uniformly mixing, using solid
The CO+H of certainty ratio2O+Ar reacting gas, flow velocity is 20～50ml/min, with 1～5 DEG C/min heating rate, opens from 100 DEG C
Begin, take a point every 25 DEG C, after insulation 30～50min, the gas component in tail gas is detected using on-line gas chromatography, and
Calculate the conversion ratio of catalytic reaction by the wherein decrement of CO.
Above-mentioned on-line gas chromatography preferably employs good fortune and founds 9790 gas chromatograpies, 5A molecular sieve chromatography post, and High Purity Hydrogen is made
For carrier gas.
For the ZnO/Cu nanocrystalline composite material of different-shape, its catalysis activity conclusion in water gas shift reation
For：1. to be respectively higher than its corresponding Cu nanocrystalline for the catalytic performance of water gas shift reation for 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 loads
Cube Cu nanocrystalline (cube ZnO/Cu) catalytic performance in water-gas shift is higher than the octahedra Cu nanometer of ZnO load
The catalytic performance of brilliant (octahedra ZnO/Cu).
Can be evident that from obtained experimental result, be closed using methods such as topological reducing process, incipient impregnations
Become to obtain the ZnO/Cu nanocrystalline composite material of different-shape, the nanocrystalline catalytic reaction of original Cu can greatly be improved
Can, there is fabulous application prospect.
In order to further illustrate the present invention, the ZnO/Cu nanocrystalline composite material that the present invention provided with reference to embodiment
And its preparation method and application be described in detail.
Embodiment 1
Cube Cu2The nanocrystalline synthesis of O
Take the CuCl of 100ml0.01mol/l with 250ml there-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 afterwards, reacts 5h.
Last centrifuge washing, vacuum drying 12h, obtain cube Cu then2O is nanocrystalline.
Its pattern is detected, sees that Fig. 1, Fig. 1 are cube Cu2The nanocrystalline SEM figure of O.
Embodiment 2
Octahedra Cu2The nanocrystalline synthesis of O
Take the CuCl of 100ml 0.01mol/l with 250ml there-necked flask2Aqueous solution is placed in oil bath pan, is subsequently added
4.44g PVP(Mw=30000), constant temperature 30min in 55 DEG C of oil baths, sequentially add afterwards 10ml 2mol/l NaOH solution and
10ml 0.6mol/l ascorbic acid solution, reacts 3h.Last centrifuge washing, vacuum drying 12h, then obtain surface and carry PVP
Protectant octahedron Cu2O is nanocrystalline.Afterwards, 150mg surface is taken to carry PVP protectant octahedron Cu2O sample is placed in tubular type
In stove, using the C of fixed proportion3H6/O2/ Ar mixed gas with flow velocity for 20ml/min pass through sample, heating rate be 5 DEG C/
Min rises to 200 DEG C from room temperature, afterwards constant temperature 30min, is more naturally down to room temperature, then obtains the clean octahedra Cu in surface2O
Nanocrystalline.
Its pattern is detected, sees that Fig. 2, Fig. 2 are octahedra Cu2The nanocrystalline SEM figure of O.
Embodiment 3
Cube ZnO/Cu2The synthesis of O nanocrystalline composite material
Take the cube Cu that above-mentioned synthesis obtains2The nanocrystalline 200mg of O is placed in monkey, prepares finite concentration simultaneously
The zinc nitrate alcohol-water solution of 0.13mol/L, takes 200 μ l incipient impregnations in cube Cu2On O is nanocrystalline, ultrasonic afterwards
30min, in exsiccator, room temperature standing places 24h, the dried powder obtaining is placed in tube furnace, under an inert atmosphere
350 DEG C of roasting 2h, heating rate is 2 DEG C/min, is finally naturally down to room temperature, then obtains cube ZnO/Cu2O is nanocrystalline multiple
Condensation material.
Above-mentioned prepare cube ZnO/Cu2The reagent adopting during O nanocrystalline composite material has zinc nitrate, dehydrated alcohol
And the experimental article such as ultra-pure water, buy gained by market
Its pattern is detected, sees that Fig. 3, Fig. 3 are cube ZnO/Cu2The nanocrystalline SEM figure of O.
ZnO/Cu to preparation2O is nanocrystalline to carry out single crystal diffraction analysis, and result is shown in that Fig. 7, Fig. 7 are the vertical of present invention preparation
Cube, octahedra two kinds of ZnO/Cu2The XRD figure 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 monkey, prepares finite concentration simultaneously
The zinc nitrate alcohol-water solution of 0.13mol/L, takes 200 μ l incipient impregnations in octahedra Cu2On O is nanocrystalline, ultrasonic afterwards
30min, in exsiccator, room temperature standing places 24h, the dried powder obtaining is placed in tube furnace, under an inert atmosphere
350 DEG C of roasting 2h, heating rate is 2 DEG C/min, is finally naturally down to room temperature, then obtains octahedra ZnO/Cu2O is nanocrystalline multiple
Condensation material.
Above-mentioned preparation octahedron ZnO/Cu2The reagent adopting during O nanocrystalline composite material has zinc nitrate, dehydrated alcohol
And the experimental article such as ultra-pure water buys gained by market
Its pattern is detected, sees that Fig. 4, Fig. 4 are octahedra ZnO/Cu2The nanocrystalline SEM figure of O.
ZnO/Cu to preparation2O is nanocrystalline to carry out single crystal diffraction analysis, and result is shown in that Fig. 7, Fig. 7 are the vertical of present invention preparation
Cube, octahedra two kinds of ZnO/Cu2The XRD figure of O and ZnO/Cu nanocrystalline composite material.
Embodiment 5
Cube ZnO/Cu nanocrystalline composite material synthesis and its in steam reacting condition catalysis activity test
Take the cube ZnO/Cu that above-mentioned synthesis obtains2O nanocrystalline composite material 100mg is placed in tube furnace, adopts 5%
CO/Ar mixed gas pass through sample with the gas flow rate of 30ml/min, then rise to 200 DEG C with the heating rate of 1 DEG C/min, afterwards
Constant temperature 1h, more naturally it is down to room temperature, then obtain cube ZnO/Cu nanocrystalline composite material, finally by the cube obtaining
ZnO/Cu is placed in vacuum drying oven and preserves.
Its pattern is detected, sees that Fig. 5, Fig. 5 are the nanocrystalline SEM figures of cube ZnO/Cu.
To preparation ZnO/Cu nanocrystalline carry out single crystal diffraction analysis, result see Fig. 7, Fig. 7 be the present invention preparation cube
Body, octahedra two kinds of ZnO/Cu2The XRD figure of O and ZnO/Cu nanocrystalline composite material.
The following is the relevant catalytic performance test that the catalyst obtained by the present embodiment is done：
The cube ZnO/Cu nanocrystalline composite material 50mg obtaining and water gas shift reation inert carrier Al2O350mg
Uniformly mix, the group of reacting gas is divided into 4.5%CO+10%H2O+85.5%Ar, reaction flow velocity is 30ml/min, heating rate
For 1 DEG C/min, each point insulation 50min, adopt a point every 25 DEG C, (good fortune founds 9790 gas phase colors by on-line gas chromatography
Spectrometer, chromatographic column is 5A molecular sieve, and carrier gas is H2) gas composition in detected gas component, and counted by the decrement of CO
Calculate the conversion ratio of reaction.
The active figure that described ZnO/Cu nanocrystalline composite material is applied to water gas shift reation is shown in Fig. 8.Experimental result finds
Which show splendid catalytic performance.
Embodiment 6
Octahedra ZnO/Cu nanocrystalline composite material synthesis and its in steam reacting condition catalysis activity test
Take the octahedra ZnO/Cu that above-mentioned synthesis obtains2O nanocrystalline composite material 100mg is placed in tube furnace, adopts 5%
CO/Ar mixed gas pass through sample with the gas flow rate of 30ml/min, then rise to 200 DEG C with the heating rate of 1 DEG C/min, here
Constant temperature 1h, is down to room temperature afterwards naturally, then obtains octahedra ZnO/Cu nanocrystalline composite material, finally by the octahedron obtaining
ZnO/Cu is placed in vacuum drying oven and preserves.
Its pattern is detected, sees that Fig. 6, Fig. 6 are the nanocrystalline SEM figures of octahedra ZnO/Cu.
To preparation ZnO/Cu nanocrystalline carry out single crystal diffraction analysis, result see Fig. 7, Fig. 7 be the present invention preparation cube
Body, octahedra two kinds of ZnO/Cu2The XRD figure of O and ZnO/Cu nanocrystalline composite material.
The following is the relevant catalytic performance test that catalyst obtained by the present embodiment is done：
The octahedra ZnO/Cu nanocrystalline composite material 50mg obtaining and water gas shift reation inert carrier Al2O350mg
Uniformly mix, the group of reacting gas is divided into 4.5%CO+10%H2O+85.5%Ar, reaction flow velocity is 30ml/min, heating rate
For 1 DEG C/min, each point insulation 50min, adopt a point every 25 DEG C, (good fortune founds 9790 gas phase colors by on-line gas chromatography
Spectrometer, chromatographic column is 5A molecular sieve, and carrier gas is H2) gas composition in detected gas component, and counted by the decrement of CO
Calculate the conversion ratio of reaction.
The active figure that described ZnO/Cu nanocrystalline composite material is applied to water gas shift reation is shown in Fig. 8.Experimental result finds
Which show splendid catalytic performance.
There is following reaction in detection of the present invention：
Cu2O+CO→Cu+CO2
Cu2O+H2→Cu+H2O
CO+H2O→CO2+H2
Example 2～6 is all buied from market using the gas (carbon monoxide, argon, propylene and oxygen etc.) arriving.
Comparative example 1
Respectively with cube Cu, octahedra Cu50mg and water gas shift reation inert carrier Al2O350mg uniformly mixes, instead
The group answering gas is divided into 4.5%CO+10%H2O+85.5%Ar, reaction flow velocity is 30ml/min, and heating rate is 1 DEG C/min,
Each point insulation 50min, adopts a point every 25 DEG C, (good fortune founds 9790 gas chromatograpies, chromatographic column by on-line gas chromatography
For 5A molecular sieve, carrier gas is H2) gas composition in detected gas component, and the conversion of reaction is calculated by the decrement of CO
Rate.
It is applied to the active figure of water gas shift reation and sees Fig. 8.
From above-described embodiment and comparative example, the ZnO/Cu nanocrystalline composite material of present invention preparation becomes for steam
Change reaction and there is excellent catalytic performance.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that it is right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (7)
1. it is characterised in that ZnO is carried on Cu nanocrystal surface, described ZnO/Cu receives a kind of ZnO/Cu nanocrystalline composite material
Rice crystal composite material is cube or octahedron.
2. the preparation method of the ZnO/Cu nanocrystalline composite material described in claim 1 is it is characterised in that comprise the following steps：
A) provide Cu2O is nanocrystalline, described Cu2O nanocrystalline for cube or octahedron；
B) using zinc nitrate as presoma, zinc nitrate is uniformly distributed in Cu by the method using incipient impregnation2O nanocrystal surface,
Roasting under an inert atmosphere, obtains ZnO/Cu2O nanocrystalline composite material；
C)ZnO/Cu2The roasting under reducing atmosphere of O nanocrystalline composite material, obtains ZnO/Cu nanocrystalline composite material；Described ZnO/
The pattern of Cu nanocrystalline composite material and described step A) in Cu2O is nanocrystalline consistent.
3. preparation method according to claim 2 is it is characterised in that described step A) it is specially：
By CuCl2Aqueous solution is reacted with NaOH solution and ascorbic acid solution, obtains Cu2O is nanocrystalline, described Cu2O nanometer
Brilliant 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 carried the protectant Cu of Polyvinylpyrrolidone2O is nanocrystalline, in C3H6/O2Roasted in/Ar mixed gas
Burn, obtain Cu2O is nanocrystalline, described Cu2O nanocrystalline for octahedron.
4. preparation method according to claim 2 is it is characterised in that described step B) it is specially：
By Cu2The method dipping zinc nitrate alcohol-water solution of O nanocrystalline employing incipient impregnation, described Cu2O is nanocrystalline and zinc nitrate
The mass volume ratio of alcohol-water solution is 1mg：1 μ l, the concentration of described zinc nitrate alcohol-water solution is (1.3 × 10-2～1.3) mol/L,
Sample after dipping, under noble gases Ar, 300 DEG C～350 DEG C carry out roasting.
5. preparation method according to claim 2 is it is characterised in that described step C) in reducing atmosphere be CO, H2Or CO
+H2O.
6. preparation method according to claim 5 is it is characterised in that described step C) it is specially：
By step B) ZnO/Cu that obtains2The roasting under reducing gas of O nanocrystalline composite material；
Described reducing gas is 1%～10%CO/Ar gaseous mixture, as described ZnO/Cu2When O nanocrystalline composite material is cube,
Described sintering temperature is 125～225 DEG C, as described ZnO/Cu2When O nanocrystalline composite material is octahedra, described sintering temperature
For 150～250 DEG C；
Or described reducing gas is 1%～10%H2/ Ar gaseous mixture, as described ZnO/Cu2O nanocrystalline composite material be cube
During body, described sintering temperature is 100～200 DEG C, as described ZnO/Cu2When O nanocrystalline composite material is octahedra, described roasting
Temperature is 125～225 DEG C；
Or described reducing gas is 1%～10%CO and 5%～15%H2O/Ar gaseous mixture, as described ZnO/Cu2O is nanocrystalline
When composite is cube, described sintering temperature is 125～225 DEG C, as described ZnO/Cu2O nanocrystalline composite material is eight
During the body of face, described sintering temperature is 150～250 DEG C.
7. the ZnO/Cu nanocrystalline composite material described in claim 1 or the preparation method system described in any one of claim 2～6
Standby ZnO/Cu nanocrystalline composite material is as the application of water gas shift reation catalyst.
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