CN106179353A - A kind of application of load-type nickel copper alloy nanocatalyst and preparation method thereof and catalytic hydrogenation - Google Patents
A kind of application of load-type nickel copper alloy nanocatalyst and preparation method thereof and catalytic hydrogenation Download PDFInfo
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- CN106179353A CN106179353A CN201610539289.3A CN201610539289A CN106179353A CN 106179353 A CN106179353 A CN 106179353A CN 201610539289 A CN201610539289 A CN 201610539289A CN 106179353 A CN106179353 A CN 106179353A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 13
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 12
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000002891 organic anions Chemical class 0.000 claims abstract description 10
- 238000009830 intercalation Methods 0.000 claims abstract description 9
- 230000002687 intercalation Effects 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229960004889 salicylic acid Drugs 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 51
- 229910052799 carbon Inorganic materials 0.000 abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 24
- 229910000792 Monel Inorganic materials 0.000 abstract description 20
- 239000002114 nanocomposite Substances 0.000 abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000002955 isolation Methods 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229910003322 NiCu Inorganic materials 0.000 description 20
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/40—
-
- B01J35/61—
-
- 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
Abstract
The invention discloses the application of a kind of load-type nickel copper alloy nanocatalyst and preparation method thereof and catalytic hydrogenation.The present invention utilizes simple coprecipitation technology self assembly in aqueous to obtain the stratiform hydroxide ambrose alloy of a large amount of organic anion intercalation as presoma, obtains the monel/carbon nano-composite catalyst of high catalytic activity and stability under inert atmosphere through step solid state heat solution in situ.The method achieve dispersed in graphitized carbon substrate of the monel nano-particle of high-crystallinity, and there is between metal and carrier strong interaction.The present invention does not use extra reducing agent, surfactant and organic solvent, reduces production cost, improves product purity.In catalytic hydrogenation reaction performance test, monel prepared by the present invention/carbon nano-composite catalyst still has higher catalytic efficiency after showing higher catalysis activity and stability, Magnetic Isolation recycle and reuse 8 times than commercialization platinum/C catalyst.
Description
Technical field
The invention belongs to chemical catalyst preparing technical field, be specifically related to a kind of load-type nickel copper alloy nanocatalyst
And preparation method thereof with the application of catalytic hydrogenation.
Background technology
Monel is widely used to commercial production as a kind of important catalyst, in order to improve its catalysis activity and
Stability, material with carbon element, aluminium oxide, silicon oxide etc. are commonly used for its carrier, but the preparation method of loaded catalyst is (such as leaching at present
Stain method, sol-gal process etc.) cost is high, complex process, needs substantial amounts of reducing agent and organic solvent, and the nano-catalytic obtained
Easily there is oxidation and reunite in agent, greatly reduces its catalytic performance, be difficult to meet modern production requirement.Therefore prepare height to urge
Change performance, low cost green catalyst significant.
In recent years, the report about synthesis load-type nickel copper alloy catalyst is of common occurrence.Document (Ding Weiping, Liu Hong, pipe
The most happy, Xue Nianhua etc. Chinese patent, 201210567980.4,2012-12-24) pass through hydro-thermal method with oleic acid as surfactant
Obtain alumina support, mix with copper nitrate solution, nickel nitrate solution, sodium hydroxide solution and hydrazine hydrate solution after roasting, and
Add a large amount of organic solvent and be made into microemulsion, product is obtained after high-temperature roasting in reducing atmosphere load-type nickel copper alloy and receives
Rice catalyst；The method complex manufacturing, cost are high, and the catalyst dispersity obtained is poor, particle size big, are difficult to be suitable for
In industrialized production.Document (Zhengdong Liu, Zongyou Yin, Zehui Du, Yang Yang, et
Al.Nanoscale, 2014,6,5110～5115) use solid carbon source by chemical vapor deposition processes, make graphene coated
To ambrose alloy oxide nanoparticle surface, and reduction obtains monel/carbon nano-composite catalyst in a hydrogen atmosphere；This is urged
Agent preparation process is complicated, and production cost is higher.Document (Hao Fang, Ming wen, Hanxing Chen, Qingsheng
Wu, et al.Nanoscale, 2016,8,536～542) synthesize graphene oxide first with Hummers method, then by its point
Being dissipated in the solution containing copper chloride, Nickel dichloride. and reducing agent, Hydrothermal Synthesis obtains monel/carbon nano-composite catalyst；
Though this catalyst higher Hydrogenation of performance, productivity is low, production cost is high, the loaded catalyst purity obtained and
Degree of crystallinity is relatively low, and metal is weak with carrier interphase interaction.
Layered double hydroxide is the anionic type laminated material that a class is important, and its laminate is by homodisperse metal
Ion forms, and interlayer is inorganic or organic anion.In recent years, nano-functional material is prepared with layered hydroxide for presoma
Report the most, be therefore expected to use it for preparing monel catalyst.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of load-type nickel copper alloy nanocatalyst.The method uses
Cheap metallic copper forms alloy with nickel, and production prices are low, has the advantages such as simple, economic, green, and is suitable for extensive raw
Produce.Prepared catalyst is applied to paranitrophenol hydrogenation reduction, and result shows that catalyst has high catalysis activity
And stability.
The present invention utilizes simple coprecipitation technology self assembly in aqueous to obtain a large amount of organic anion (can to make
For carbon source and reducing agent) the stratiform hydroxide ambrose alloy of intercalation is as presoma, through step solid-state pyrolysis in situ under inert atmosphere
Obtain the monel/carbon nano-composite catalyst of high catalytic activity and stability.Monel/carbon prepared by solid state heat solution
Nano-composite catalyst has bigger specific surface area, higher purity and degree of crystallinity so that it is show high catalysis activity；
Strong interaction between homodisperse monel nanoparticle and carbon carrier, maintains the steady of supported catalyst structure
Qualitative.Reclaimed by simple Magnetic Isolation, recycling of catalyst can be realized.
The preparation method of load-type nickel copper alloy nanocatalyst of the present invention is:
1) it is 0.1-0.2mol L by 50mL concentration-1Nickel salt aqueous solution, 50mL concentration be 0.02-0.1mol L-1's
Copper salt solution and 50mL concentration are 0.1-0.5mol L-1Aqueous solutions of organic salts uniformly mix, be slowly added to 50mL after stirring
Concentration is 1.0-5.0mol L-1Aqueous solution of urea, at 80-100 DEG C in inert atmosphere react 24-48 hour, product through from
The heart, washing also obtain the stratiform hydroxide ambrose alloy presoma of organic anion intercalation after drying；
2) by step 1) presoma prepared 500-700 DEG C of roasting 0.5-3 hour in inert atmosphere, i.e. obtain support type
Monel nanocatalyst.
Described nickel salt is selected from Ni (NO3)2、NiCl2、NiSO4In one or both.
Described mantoquita is selected from Cu (NO3)2、CuCl2、CuSO4In one or both.
Described nickel ion is 1-5:1 with the mol ratio of copper ion.
Described organic salt is in sodium benzoate, sodium salicylate, sodium ethylene diamine tetracetate, dodecylbenzene sodium sulfonate
One or more.
Described inert atmosphere is nitrogen and/or argon gas atmosphere.
The load-type nickel copper alloy nanocatalyst prepared by said method is applied to be catalyzed paranitrophenol hydrogenation
Reduction reaction: 5-20mg load-type nickel copper alloy nanocatalyst is distributed to the p-nitrophenyl phenol solution of 100mL 0.01-1mM
In, it is subsequently adding 0.01-1g sodium borohydride and starts reaction.
Monel prepared by the present invention/carbon nano-composite catalyst achieves the monel nano-particle of high-crystallinity
Dispersed in graphitized carbon substrate, and there is between metal and carrier strong interaction.The present invention does not use extra
Reducing agent, surfactant and organic solvent, reduce production cost, improves product purity.In catalytic hydrogenation reaction performance
In test, monel of the present invention/carbon nano-composite catalyst shows higher than commercialization platinum/C catalyst
Catalysis activity and stability, in catalyst, the existence of Ni element makes it can carry out Magnetic Isolation recycle and reuse, Magnetic Isolation
After recycle and reuse 8 times, this catalyst still has higher catalytic efficiency.Compared with prior art, of the present invention
Preparation method has the feature such as abundant raw material source, simple, the production process greenization of preparation technology, and the catalyst of preparation has
High catalytic activity and stability, have wide prospects for commercial application.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic diagram that solid state heat solution preocess prepares NiCu/C nano-composite catalyst.
Accompanying drawing 2 is stratiform hydroxide ambrose alloy presoma and the stereoscan photograph of NiCu/C nano-composite catalyst.
Accompanying drawing 3 is NiCu/C nano-composite catalyst transmission electron microscope and high-resolution-ration transmission electric-lens photo.
Accompanying drawing 4 is the X-ray diffraction spectrogram of NiCu/C nano-composite catalyst.
Accompanying drawing 5 is the Raman spectrogram of NiCu/C nano-composite catalyst.
Accompanying drawing 6 is the XPS spectrum figure of NiCu/C nano-composite catalyst.
Accompanying drawing 7 is the uv-vis spectra of NiCu/C nano-composite catalyst paranitrophenol Catalytic Hydrogenation Properties test
Figure.
Accompanying drawing 8 is NiCu/C, the Ni/C and commercialization Pt/C first-order kinetics curve pair in catalytic hydrogenation reaction
Than figure.
Accompanying drawing 9 is the hysteresis curve of NiCu/C nano-composite catalyst.
Accompanying drawing 10 be NiCu/C nano-composite catalyst recycle block diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, preparation method of the present invention is described further, but the guarantor of the present invention
The scope of protecting is not limited to this.
Embodiment 1
1) it is 0.15mol L by 50mL concentration-1Nickel nitrate, 50mL concentration be 0.05mol L-1Copper nitrate aqueous solution
It is 0.4mol L with 50mL concentration-1Sodium salicylate aqueous solution uniformly mix, being slowly added to 50mL concentration after stirring 10 minutes is
2.0mol·L-1Aqueous solution of urea, at 95 DEG C in nitrogen atmosphere react 36 hours, product by centrifugation, washing and obtain after drying
The stratiform hydroxide ambrose alloy presoma of a large amount of organic anion intercalations, stereoscan photograph is shown in Fig. 2；
2) presoma above-mentioned steps prepared 500 DEG C of roastings in nitrogen atmosphere obtain monel/carbon nanometer for 1 hour
Composite catalyst, is designated as NiCu/C, and characterization result is shown in Fig. 2-6, and product is evaluated for paranitrophenol Catalytic Hydrogenation Properties.
Embodiment 2
1) it is 0.12mol L by 50mL concentration-1Nickel nitrate, 50mL concentration be 0.08mol L-1Copper nitrate aqueous solution
It is 0.4mol L with 50mL concentration-1Sodium salicylate aqueous solution uniformly mix, being slowly added to 50mL concentration after stirring 10 minutes is
2.0mol·L-1Aqueous solution of urea, at 95 DEG C in argon gas atmosphere react 36 hours, product by centrifugation, washing and obtain after drying
The stratiform hydroxide ambrose alloy presoma of a large amount of organic anion intercalations；
2) presoma above-mentioned steps prepared 700 DEG C of roastings in nitrogen atmosphere obtain monel/carbon nanometer for 2 hours
Composite catalyst, is designated as NiCu/C-1, characterization result such as Fig. 4 and Fig. 5, and product is commented for paranitrophenol Catalytic Hydrogenation Properties
Valency.
Embodiment 3
1) it is 0.1mol L by 50mL concentration-1Nickel nitrate, 50mL concentration be 0.1mol L-1Copper nitrate aqueous solution and
50mL concentration is 0.4mol L-1Sodium salicylate aqueous solution uniformly mix, being slowly added to 50mL concentration after stirring 10 minutes is
1.5mol·L-1Aqueous solution of urea, at 95 DEG C in nitrogen atmosphere react 48 hours, product by centrifugation, washing and obtain after drying
The stratiform hydroxide ambrose alloy presoma of a large amount of organic anion intercalations；
2) presoma above-mentioned steps prepared 600 DEG C of roastings in nitrogen atmosphere obtain monel/carbon nanometer for 1 hour
Composite catalyst, is designated as NiCu/C-2, and characterization result is shown in Fig. 4 and Fig. 5, and product is commented for paranitrophenol Catalytic Hydrogenation Properties
Valency.
Comparative example 1
1) it is 0.2mol L by 100mL concentration-1Nickel nitrate aqueous solution and 50mL concentration be 0.4mol L-1Bigcatkin willow
Acid sodium aqueous solution uniformly mixes, and being slowly added to 50mL concentration after stirring 10 minutes is 2.0mol L-1Aqueous solution of urea, 90 DEG C
Lower nitrogen atmosphere reacts 36 hours, product by centrifugation, washing obtain the stratiform hydrogen of a large amount of organic anion intercalation after drying
Nickel oxide precursor；
2) presoma above-mentioned steps prepared 500 DEG C of roastings 1 hour in nitrogen atmosphere, is designated as Ni/C, and product is used for
Paranitrophenol Catalytic Hydrogenation Properties is evaluated.
Comparative example 2
1) it is 0.2mol L by 100mL concentration-1Nickel nitrate aqueous solution and 50mL concentration be 0.3mol L-1Benzene first
Acid sodium aqueous solution uniformly mixes, and being slowly added to 50mL concentration after stirring 10 minutes is 1.0mol L-1Aqueous solution of urea, 90 DEG C
Lower nitrogen atmosphere reacts 48 hours, product by centrifugation, washing obtain the stratiform hydrogen of a large amount of organic anion intercalation after drying
Nickel oxide precursor；
2) presoma above-mentioned steps prepared 700 DEG C of roastings 2 hours in argon gas atmosphere, are designated as Ni/C-1, and product is used
Evaluate in paranitrophenol Catalytic Hydrogenation Properties.
Application examples 1
20mg catalyst (NiCu/C, Ni/C and Pt/C) is distributed to respectively the p-nitrophenyl phenol solution of 100mL0.2mM
In, add 0.1g sodium borohydride and start timing, taking a sample every 30 seconds, examined by ultraviolet-uisible spectrophotometer after filtration
Surveying its absorbance, and calculate its reaction rate constant by First-order kinetics equation, result is as shown in Fig. 7, Fig. 8 and Biao 1.
After NiCu/C catalyst Magnetic Isolation being reclaimed, after recycling 8 times (as shown in Figure 10), catalyst still has higher urging
Change activity.
Application examples 2
10mg catalyst (NiCu/C, Ni/C and Pt/C) is distributed to respectively the p-nitrophenyl phenol solution of 100mL0.2mM
In, add 0.1g sodium borohydride and start timing, taking a sample every 30 seconds, examined by ultraviolet-uisible spectrophotometer after filtration
Survey its absorbance, and calculate its reaction rate constant by First-order kinetics equation.
The presoma of catalyst is three-dimensional flower ball-shaped as seen from Figure 2, and roasting reduction afterproduct pattern still keeps；Figure
3 high-resolution-ration transmission electric-lens photos are it can be clearly seen that the lattice fringe of lattice fringe monel (111) crystal face, and between striped
Away from for 0.21nm；Meanwhile, graphitization obtains carbon-coating and is coated on around monel nano-particle, effectively prevent entering of metal dimension
One step increases；XRD and Raman spectrum shows the existence of monel and graphitized carbon, and products pure, and degree of crystallinity is high, graphite
The existence changing carbon not only increases the specific surface area of product, and is conducive to electric transmission in catalytic reaction process；Shown in Fig. 6
XPS result shows that carbon surface contains abundant oxy radical, has strong interaction, be all conducive to its catalysis between carbon carrier and metal
Activity and stability.Catalytic performance test result shows that NiCu/C nano-composite catalyst has more than commercialization Pt/C catalyst
High catalysis activity, and can Magnetic Isolation recycle and reuse, there is the highest industrial application value.
As a comparison nickel catalyst carried, is added without mantoquita in preparation process, other steps are same as described above, sample
Product are designated as Ni/C.Platinum/C catalyst as a comparison, purchased from commercialization channel, sample is designated as Pt/C.
Reaction result shows, when catalyst charge is 20mg, NiCu/C, Ni/C and commercialization Pt/C catalyst are by right
Nitrophenol reduction is respectively necessary for 90s, 180s and 360s, and corresponding first order kinetics reaction rate constant is respectively 0.032s-1、
0.018s-1、0.0078s-1(as shown in Fig. 8, table 1).As can be seen here, the catalytic activity order of three kinds of catalyst is: NiCu/C >
Ni/C > commercialization Pt/C.After NiCu/C catalyst is carried out Magnetic Isolation recovery, still show good catalytic hydrogenation effect.
Table 1
Claims (8)
1. the preparation method of a load-type nickel copper alloy nanocatalyst, it is characterised in that its concrete operation step is:
1) it is 0.1-0.2mol L by 50mL concentration-1Nickel salt aqueous solution, 50mL concentration be 0.02-0.1mol L-1Mantoquita
Aqueous solution and 50mL concentration are 0.1-0.5mol L-1Aqueous solutions of organic salts uniformly mix, be slowly added to 50mL concentration after stirring
For 1.0-5.0mol L-1Aqueous solution of urea, at 80-100 DEG C in inert atmosphere react 24-48 hour, product by centrifugation, wash
Wash and obtain after drying the stratiform hydroxide ambrose alloy presoma of organic anion intercalation；
2) by step 1) presoma prepared 500-700 DEG C of roasting 0.5-3 hour in inert atmosphere, i.e. obtain support type ambrose alloy
Alloy nano catalyst.
Preparation method the most according to claim 1, it is characterised in that described nickel salt is selected from Ni (NO3)2、NiCl2、NiSO4
In one or both.
Preparation method the most according to claim 1, it is characterised in that described mantoquita is selected from Cu (NO3)2、CuCl2、CuSO4
In one or both.
Preparation method the most according to claim 1, it is characterised in that described nickel is 1-5:1 with the mol ratio of copper.
Preparation method the most according to claim 1, it is characterised in that described organic salt is selected from sodium benzoate, salicylic acid
One or more in sodium, sodium ethylene diamine tetracetate, dodecylbenzene sodium sulfonate.
Preparation method the most according to claim 1, it is characterised in that described inert atmosphere is nitrogen and/or argon gas
Atmosphere.
7. the load-type nickel copper alloy nanocatalyst prepared according to the arbitrary described method of claim 1-6 is catalyzed nitre
The application of base phenol hydrogenation reduction reaction.
Application the most according to claim 7, it is characterised in that its concrete reaction condition is: by 5-20mg support type ambrose alloy
Alloy nano catalyst is distributed in the p-nitrophenyl phenol solution of 100mL 0.01-1mM, is subsequently adding 0.01-1g sodium borohydride
Start reaction.
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