CN108355661A - A kind of threadiness Cu-Ni alloy nanometer crystals and its synthetic method - Google Patents
A kind of threadiness Cu-Ni alloy nanometer crystals and its synthetic method Download PDFInfo
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- CN108355661A CN108355661A CN201810004328.9A CN201810004328A CN108355661A CN 108355661 A CN108355661 A CN 108355661A CN 201810004328 A CN201810004328 A CN 201810004328A CN 108355661 A CN108355661 A CN 108355661A
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- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 229910002482 Cu–Ni Inorganic materials 0.000 title claims description 27
- 229910045601 alloy Inorganic materials 0.000 title claims description 27
- 239000000956 alloy Substances 0.000 title claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- QYJPSWYYEKYVEJ-FDGPNNRMSA-L copper;(z)-4-oxopent-2-en-2-olate Chemical compound [Cu+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QYJPSWYYEKYVEJ-FDGPNNRMSA-L 0.000 claims abstract description 6
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims abstract description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910000990 Ni alloy Inorganic materials 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 206010068150 Acoustic shock Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention discloses a kind of threadiness Cu Ni alloy nanometer crystals and its synthetic methods.This is nanocrystalline to be made of threadiness, has face-centred cubic structure;It is reducing agent by covering, aniline of polyvinylpyrrolidone PVP, itself and cupric acetylacetonate, acetopyruvic acid nickel is dissolved in benzyl alcohol, prepared by solvent-thermal method.As a result it shows:The addition of appropriate PVP and a small amount of aniline, nano-particle is enable to orient the linear nanostructure of composition, and with certain special exposure crystal faces and a large amount of twin dislocation, more active sites can be provided to be nanocrystalline, exhaust-gas treatment can be effectively realized as catalyst, realize organic matter degradation in waste water.The success of this nanometer of crystal preparation method, the controlledly synthesis to nanocrystalline pattern, transition metal, the controlledly synthesis of bimetal nano crystalline substance and the application of the nanocrystalline catalytic performance of special appearance have certain theory and practice meaning.
Description
Technical field
The present invention relates to metal nano controlledly synthesis fields, more specifically to a kind of threadiness Cu-Ni alloy nanometer crystals
And its synthetic method, this is nanocrystalline to can be used for the catalytic fields such as catalysis oxidation exhaust gas, degrading waste water organic matter.
Background technology
Nano material has the study on the synthesis that special property drives researcher to be dedicated to various nano-particles, examination
Figure changes the physical property and chemical property of nano-particle by changing pattern, size of nano-particle etc., this is synthetic
The excellent nanocatalyst of energy provides feasible theoretical foundation.Bimetal nano crystalline substance is made of two kinds of different metal elements, both
Possess the property of each constituent element, and the singular effects generated with the synergistic effect between heteroatom.Not due to two kinds
The bimetallic of same metal composition has the common energy band of two components, is formed in the alloy by changing metal, thus it is possible to vary gold
The geometric configuration and electronic structure for belonging to particle surface, can additionally adjust the distance between metal d bands and Fermi energy levels, change
The adsorption capacity for becoming nano-particle, influences the activity, selectivity and stability of nano metal activity phase.Different-shape is different sudden and violent
The metallic catalyst for revealing crystal face has visibly different electronic configuration in their superficial layer, while these different crystal faces have different stand
Body structure, so as to cause the different adsorption energy of the reaction product in heterogeneous catalysis or intermediate product.Therefore, pattern control is for list
Metal and bimetallic are all extremely important.
Most in the latest 20 years, in relation in the constantly incremental research of bimetal nano crystalline substance, many different structures, pattern are received
Rice bimetallic has been successfully synthesized, such as polyhedron monocrystalline and polycrystalline, nanometer rods, nano wire, nanometer be dendritic, more pod-like, hollow
Bimetallic core-shell structure, heterojunction structure and alloy structure of structure, concave structure etc. etc. had been reported that.But double
In metal controlledly synthesis, the controlledly synthesis of the bimetal nano crystalline substance of transition metal is but seldom reported.This is mainly due to transition
Metal potential is relatively low, is being nucleated and is needing very strong reducing agent that transition metal ions is reduced into zero-valent state original in growth course
Son, and the strong reducing agent of reducing property, which is added, can cause kinetics process to be difficult to control.
Therefore, linear Cu-Ni alloy nanometer crystals (having more Active site structures) are controllably prepared, while taking into account and synthesizing
Journey is simple and practicable and with the synthetic method of covering cheap and easy to get, then is particularly important.
Invention content
Technical problem:There is difference to prepare in order to which controlledly synthesis goes out the bimetal nano crystalline substance of different-shape transition metal
The nano material of characteristic, the present invention propose a kind of threadiness Cu-Ni alloy nanometer crystals and its synthetic method.It is the center of area that this is nanocrystalline
Cubic is uniformly dispersed, and presentation nanometer is linear, a diameter of 35~50 nanometers, and length is hundreds of nanometers to tens microns;With poly-
Vinylpyrrolidone PVP is covering, aniline is the synthesis of reducing agent qualitative, quantitative.Because its with certain special exposure crystal faces with
And a large amount of twin dislocation, more active sites can be provided, thus can be used for being prepared into catalyst, in catalysis oxidation exhaust gas, drop
There is very strong application prospect in the fields such as solution wastewater through organic matter.
Technical solution:The linear Cu-Ni alloy nanometer crystals of the present invention are face-centered cubic crystal form, are uniformly dispersed, and nanometer is presented
Threadiness, a diameter of 35~50 nanometers, length is hundreds of nanometers to tens microns.
The synthetic method of the linear Cu-Ni alloy nanometer crystals of the present invention is using benzyl alcohol as solvent, polyvinylpyrrolidone PVP
For covering, aniline is reducing agent, and specific building-up process is as follows:
A. at room temperature, cupric acetylacetonate, acetopyruvic acid nickel, polyvinylpyrrolidone PVP are dissolved in benzyl alcohol and are stirred
It mixes, aniline is added dropwise in whipping process, carrying out being ultrasonically treated later makes solution be uniformly mixed;
B. it moves into autoclave and reacts after being ultrasonically treated;Cooled to room temperature after reaction, by products therefrom through super
Acoustic shock swings, centrifuge washing, freeze-drying is to get linear Cu-Ni alloy nanometer crystals.
Wherein, volume fraction of the aniline in reaction solution is 2~50%.
A concentration of 0.05~the 0.5mmol/L of polyvinylpyrrolidone PVP.
The molar ratio of the cupric acetylacetonate and acetopyruvic acid nickel is 1:0.5~1:2, cupric acetylacetonate with it is poly-
The molar ratio of vinylpyrrolidone PVP is 1:0.002~1:0.02.
It is 150~220 DEG C of 5~20h of maintenance that the temperature reacted in autoclave is moved into after the supersound process.
Exactly Cu, Ni precursor solution exist under aniline reducing agent, the effect that polyvinylpyrrolidone PVP is covering
Thermostatic crystallization in autoclave, obtained nano-particle uniformly assemble, obviously do not agglomerate and be piled into nanometer blocks.Follow-up
Freeze-drying under, the effect of caving in of nano particle internal gutter structure falls below minimum, and obtained nanoparticle activated position is more
It is more.The nanocrystalline catalyst that can be used for preparation and there is sp act, for necks such as catalysis oxidation exhaust gas, degrading waste water organic matters
Domain.
Advantageous effect:First, polyvinylpyrrolidone PVP, aniline itself are common basic organic solvents, inexpensive easy
.Secondly, after PVP is introduced, in nucleation stage oriented attachment on nano-particle, certain spies are adsorbed in growth course later
On fixed crystal face;And aniline also has the function of inhibiting to increase to influence kinetics, phenyl function simultaneously as reducing agent
Group's molecules influence can prevent its growth in certain particular crystal planes in nanocrystalline forming process, to make growth be
Linear Nanoalloy.When being used as catalyst, since their superficial layer has visibly different electronic configuration, cause more
Reaction product or the different adsorption energy of intermediate product in being mutually catalyzed;In addition, since linear Nanoalloy has certain special exposures
Crystal face has a good activity to certain redox reactions, at the same this special appearance it is nanocrystalline in there is a large amount of
Twin dislocation can provide many active sites, to effectively improve the catalytic activity of catalyst for it.
Description of the drawings
Fig. 1 is the XRD diagram of threadiness Cu-Ni alloy nanometer crystals in case study on implementation 1.
Fig. 2 is threadiness Cu-Ni alloy nanometer crystals electron microscopes in case study on implementation 1:(a) it is that SEM schemes, is (b) that TEM schemes.
Specific implementation mode
1 threadiness Cu-Ni alloy nanometer crystals of embodiment prepare catalyst oxidation organic exhaust gas
1. preparing threadiness Cu-Ni alloy nanometer crystals
By 0.1mmol cupric acetylacetonates, the polyvinylpyrrolidine of 0.1mmol acetopyruvic acids nickel and 0.1mmol/L
Ketone PVP, which is dissolved in the benzyl alcohol of 15ml, stirs 10min, and 0.5ml aniline is added dropwise in whipping process, carries out at ultrasound later
Reason 10min makes solution be uniformly mixed.Mixed solution is moved into the autoclave of 25ml after supersound process, 200 DEG C of maintenances
12h.Products therefrom is cleaned and is centrifuged with acetone by cooled to room temperature, is centrifuged with the centrifugal speed of 10000r/min
8min is cleaned several times with the mixed liquor of absolute ethyl alcohol and acetone later.The product that centrifugation obtains finally is put into freeze drying box
It is dry.
2. preparing supported catalyst, and carry out organic exhaust gas Degrading experiment
It weighs Cu-Ni nano wires made from 0.09g and the mesoporous ZSM-5 zeolite mixing of 1.0g is scattered in 10ml ethyl alcohol, surpass
The good mixed liquor of ultrasonic mixing is placed on and dries at room temperature by sonication 4h, puts it into 80 DEG C of holding 12h in baking oven later, then
Carry out temperature programming processing, 2 ° of min-1Rise to 450 DEG C of holding 4h.Catalyst activity phase content is 11wt%.
Ortho-xylene catalytic combustion activity evaluation is carried out in normal pressure quartz tube reactor (internal diameter 10mm).By catalyst
Sample activates 1h in air atmosphere at 450 DEG C, starts catalyst combustion reaction when then naturally cooling to 100 DEG C.Air all the way
(78.84ml/min) is passed through the bubbler equipped with ortho-xylene, after then being mixed with another way air (121.16ml/min), into
Enter reactor.Bubbler temperature control is at 0 DEG C, and the total flow of air is 200ml/min, corresponding reactor total volume air speed
(GHSV) it is about 10000h-1(relative to entire monolithic catalyst volume), ortho-xylene volume fraction is about in reaction gas
1000ppm。
T10And T90(o-xylene conversion is respectively the temperature corresponding to 10% and 90%) indicates the beginning of ortho-xylene
Reaction temperature and complete conversion temperature.The result shows that catalyst T prepared by threadiness Cu-Ni alloy nanometer crystals10And T90Have significant
Decline, the catalyst prepared better than conventional method.
2 threadiness Cu-Ni alloy nanometer crystals of embodiment prepare catalyst reduction methylene blue
1. preparing threadiness Cu-Ni alloy nanometer crystals
By 0.15mmol cupric acetylacetonates, the polyvinyl pyrrole of 0.075mmol acetopyruvic acids nickel and 0.2mmol/L
Alkanone PVP, which is dissolved in the benzyl alcohol of 15ml, stirs 10min, and 1ml aniline is added dropwise in whipping process, carries out at ultrasound later
Reason 10min makes solution be uniformly mixed.Mixed solution is moved into the autoclave of 25ml after supersound process, 175 DEG C of maintenance 8h.
Products therefrom is cleaned and is centrifuged with acetone by cooled to room temperature, and 8min is centrifuged with the centrifugal speed of 10000r/min,
It is cleaned several times with the mixed liquor of absolute ethyl alcohol and acetone later.The product that centrifugation obtains finally is put into freeze drying box drying.
2. catalysis reduction methylene blue test
2ml NaBH are added in 100mL methylene blues4, 0.1g threadiness Cu-Ni alloy nanometer crystals are added later.Addition is received
It after meter Jing Yi minutes, is found by ultraviolet spectra, represents methylene blue and NaBH4Characteristic peak 664nm rapidly disappear, significantly plus
Fast reduction reaction speed.
3 threadiness Cu-Ni alloy nanometer crystals of embodiment prepare catalyst p-nitrophenol
1. preparing threadiness Cu-Ni alloy nanometer crystals
By 0.225mmol cupric acetylacetonates, the polyvinyl pyrrole of 0.45mmol acetopyruvic acids nickel and 0.3mmol/L
Alkanone PVP, which is dissolved in the benzyl alcohol of 15ml, stirs 10min, and 1.5ml aniline is added dropwise in whipping process, carries out ultrasound later
Processing 10min makes solution be uniformly mixed.Mixed solution is moved into the autoclave of 25ml after supersound process, 220 DEG C of maintenances
16h.Products therefrom is cleaned and is centrifuged with acetone by cooled to room temperature, is centrifuged with the centrifugal speed of 10000r/min
8min is cleaned several times with the mixed liquor of absolute ethyl alcohol and acetone later.The product that centrifugation obtains finally is put into freeze drying box
It is dry.
2. p-nitrophenol catalytic hydrogenation reaction
It weighs that 2.0g p-nitrophenols, 0.08g Cu-Ni be nanocrystalline and 100ml absolute ethyl alcohols is to agitating function
In stainless steel cauldron, the air being passed through in high pure nitrogen 10min displacement reaction systems, being passed through High Purity Hydrogen to pressure later is
0.8Mpa.100 DEG C are warming up under the conditions of 600r/min, reaction a period of time.It is cooled to room temperature after reaction, using efficient
P-nitrophenol and p-aminophenol content in liquid-phase chromatographic analysis product.The experimental results showed that after reacting 6h, p-nitrophenol
Conversion ratio reached 99%, catalytic activity is obviously improved compared to other catalyst.
Claims (6)
1. a kind of threadiness Cu-Ni alloy nanometer crystals, which is characterized in that it is face-centered cubic crystal form that this is nanocrystalline, is uniformly dispersed, and is presented
Nanometer is linear, a diameter of 35~50 nanometers, and length is hundreds of nanometers to tens microns.
2. a kind of synthetic method of threadiness Cu-Ni alloy nanometer crystals as described in claim 1, which is characterized in that specifically synthesized
Journey is as follows:
A. at room temperature, cupric acetylacetonate, acetopyruvic acid nickel, polyvinylpyrrolidone PVP are dissolved in benzyl alcohol and are stirred,
Aniline is added dropwise in whipping process, carrying out being ultrasonically treated later makes solution be uniformly mixed;
B. it moves into autoclave and reacts after being ultrasonically treated;Cooled to room temperature after reaction shakes products therefrom through ultrasound
It swings, centrifuge washing, freeze-drying is to get linear Cu-Ni alloy nanometer crystals.
3. the synthetic method of threadiness Cu-Ni alloy nanometer crystals according to claim 2, which is characterized in that the aniline exists
Volume fraction in reaction solution is 2~50%.
4. the synthetic method of threadiness Cu-Ni alloy nanometer crystals according to claim 2, which is characterized in that the polyethylene
A concentration of 0.05~0.5mmol/L of pyrrolidones PVP.
5. the synthetic method of threadiness Cu-Ni alloy nanometer crystals according to claim 2, which is characterized in that the levulinic
The molar ratio of ketone acid copper and acetopyruvic acid nickel is 1:0.5~1:2, cupric acetylacetonate is with polyvinylpyrrolidone PVP's
Molar ratio is 1:0.002~1:0.02.
6. the synthetic method of threadiness Cu-Ni alloy nanometer crystals according to claim 2, which is characterized in that at the ultrasound
It is 150~220 DEG C of 5~20h of maintenance that the temperature reacted in autoclave is moved into after reason.
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