CN102909034A - Preparation of supported gold-nickel alloy nanocatalyst - Google Patents
Preparation of supported gold-nickel alloy nanocatalyst Download PDFInfo
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- CN102909034A CN102909034A CN201110222260XA CN201110222260A CN102909034A CN 102909034 A CN102909034 A CN 102909034A CN 201110222260X A CN201110222260X A CN 201110222260XA CN 201110222260 A CN201110222260 A CN 201110222260A CN 102909034 A CN102909034 A CN 102909034A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 19
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000011943 nanocatalyst Substances 0.000 title description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000010931 gold Substances 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 35
- 229910052737 gold Inorganic materials 0.000 claims abstract description 31
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 230000000536 complexating effect Effects 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract 3
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 13
- 229910000085 borane Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 238000010668 complexation reaction Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 21
- 239000000956 alloy Substances 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 37
- 229910021641 deionized water Inorganic materials 0.000 description 37
- 239000007787 solid Substances 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910002711 AuNi Inorganic materials 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 229910017398 Au—Ni Inorganic materials 0.000 description 5
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- BTKXSYWWRGMQHR-UHFFFAOYSA-N [amino(diethoxy)silyl]oxyethane Chemical compound CCO[Si](N)(OCC)OCC BTKXSYWWRGMQHR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 229910018493 Ni—K Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nitryl aromatic alkene Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention relates to preparation of supported gold-nickel alloy nanoparticles. The preparation comprises the following steps of: grafting a radical capable of complexing metal ions on a carrier which is rich in hydroxyl functional groups on the surface; complexing alloy and reducing to prepare gold nanoparticles; adsorbing nickel ions by using the gold nanoparticles as cores and catalyzing reduction of nickel together with a weak reducing agent; performing air roasting and hydrogen high-temperature treatment to obtain gold-nickel alloy nanoparticles, wherein the total metal weight supporting capacity of the catalyst is 0.1-10 percent, and the molar ratio of nickel to the gold is 0.001-5. According to the preparation, a nucleation center is provided for the nickel by the gold nanoparticles prepared by the first step and the reduction in the case of a weak reducing agent is catalyzed, the gold-nickel alloy nanoparticles with high thermal stability and high dispersion capacity are prepared on the carrier, and the average particle size is 3.5 nm. The catalyst shows higher activity than that of a single-metal gold catalyst in carbon monoxide reaction.
Description
Technical field
The present invention relates to a kind of preparation of golden nickel alloy nanocatalyst, is a kind of preparation of loaded golden nickel alloy nano particle specifically.
Background technology
To show the activity and selectivity that is better than single-metal reforming catalyst in a lot of reactions more and more noticeable because of it for alloy catalyst.Since understanding that the preparation method (JP60238148 and JP0194945) of supported nano Au catalyst, nano-Au catalyst are found in the reactions such as selective hydrogenation of selective oxidation, propylene ring oxidation reaction and nitryl aromatic alkene of CO low temperature oxidation, alcohol, the human hairs such as Haruta of Japan show peculiar catalytic performance.Raney nickel reveals high activity (CN1415413) in a lot of hydrogenation reactions such as reaction tables such as aromatic hydrogenation, solvent oil hydrogenations.Recently, the block AuNi alloy with cavernous structure of electrochemical production shows the activity (Journal of Alloys and Compounds 509 (2011) L47-L51) that is better than 3 times more than of block AuNi alloys in the reaction of electrochemical process oxidation carbohydrate.
CN101920210A has introduced a kind of efficient nanocatalyst Au-VSB-5 for the CO catalytic oxidation, adopts inorganic chlorate, and phosphoric acid is raw material, and organic amine is template, and water is that solvent has synthesized nano-pore nickel phosphate nanocrystal.Synthetic nano-pore nickel phosphate nanocrystalline powder is put into the inorganic salt solution of the gold for preparing, gold particle is introduced among the duct, mist reduction through hydrogen and nitrogen makes size uniform, and the significant nm of gold of quantum effect is carried on the composite among the nano-pore duct.But the state of not mentioning Au and Ni is alloy state whether.
CN1037072C has introduced a kind of preparation of particle Ni-Pd alloy catalyst, in vacuum chamber, the nickel plate is put on the anode, the palladium thin slice press with the nickel plate on, utilize electric arc that nickle atom and palladium atom are run foul of each other, preparation nanometer NiPd alloy ultro-micro partical catalyst.
In sum, the present report that does not also have about the preparation method of loaded AuNi alloy nano particle.Because the fusing point of Au is lower, when high-temperature process, assemble easily, and Ni belongs to refractory metal, not only can improve the stability of Au by forming the AuNi alloy, and can reduce the cost of catalyst; In addition, form in some reactions, can show behind the alloy and be better than the active or selective of single-metal reforming catalyst; And AuNi sees from phasor and is not easy to form alloy.Therefore synthetic a kind of loaded AuNi alloy nano catalyst has great importance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of loaded golden nickel alloy nano particle.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of preparation method of loaded golden nickel alloy nano particle, grafting amino functional group on the carrier of rich surface hydroxyl functional group, make golden nanometer particle by the complexing gold and with its reduction again, again take golden nanometer particle as nuclear absorbed Ni ion and with the reduction of weak reductant catalytic nickel, through obtaining golden nickel alloy nano particle after air roasting and the hydrogen high-temperature process, the actual loading of gold and nickel and molar ratio and inventory and rate of charge approach in the catalyst that makes, total weight metal loading of catalyst is 0.1-10%, and the mol ratio of nickel and gold is at 0.001-5.Gold nickel alloy nano particle high degree of dispersion and has high thermal stability on carrier, behind air roasting and hydrogen reducing, the average grain diameter of particle is 3.5nm, and narrow size distribution.This catalyst shows the high activity that is higher than the monometallic Au catalyst in reaction of carbon monoxide.
The concrete operations condition is as follows:
1) surface is contained the carrier that enriches hydroxyl according to the ratio of the corresponding 1-4ml aminosilane reagents of 1g carrier under the organic solvent condition 60-100 ℃ backflow 2-48 hour, filter and use organic solvent washing, dried 1-6 hour for 40-80 ℃, obtain the carrier of surface amination;
2) in the time of 0-40 ℃, the aqueous solution that carrier is joined the predecessor of gold carries out complexing, after filtration after the washing, add an amount of strong reductant reduction, after filtration after the washing, with containing in the predecessor aqueous solution that golden carrier is distributed to nickel of obtaining, the ratio of nickel and gold is at 0.001-5, add simultaneously the reduction of an amount of weak reductant, after filtration after the washing, with pressed powder through drying at room temperature, again through 60-120 ℃ of oven dry, 350-600 ℃ of air roasting, 500-700 ℃ of hydrogen reducing obtains loaded golden nickel alloy nano particle.
Described 350-600 ℃ of air roasting process is: the material after will drying rises to 350-600 ℃ with the programming rate of 1-10 ℃/min, and remains in 350-600 ℃ the air roasting 3-10 hour;
Described 500-700 ℃ of hydrogen reducing process is: the material behind the air roasting is risen to 500-700 ℃ with the programming rate of 1-20 ℃/min, and remained in 500-700 ℃ the hydrogen reduction 1-5 hour;
Described strong reductant is hydrazine hydrate or sodium borohydride.
Described weak reductant is organo-borane, for example, and the tert-butylamine borine.
The concentration of aqueous solution of reducing agent is at 0.001-5molL
-1
The present invention carries out the complexing of nickel ion and the predecessor reduction process of nickel simultaneously, and does not carry out the washing and filtering operation after the nickel ion complexing, makes actual loading and the inventory of nickel suitable; Simultaneously reduction process take golden nanometer particle as nuclear absorption and with weak reductant together catalytic nickel reduce in gold surface, through making nickel and gold be completed into alloy behind roasting and the hydrogen reducing;
In the situation that does not have golden nanometer particle to exist, weak reductant can not reduce nickel; And when this adopts strong reductant that nickel is reduced, the carrier surface that the nickel of reduction has most of physical absorption to exist in non-golden nanometer particle, only has the small part chemisorbed in the golden nanometer particle surface, there is a large amount of nickel simple substance to exist behind process roasting and the hydrogen reducing, and only has a small amount of nickel and gold to form alloy.
Described organic solvent is one or more in benzene, toluene, ethanol, the cyclohexane, described aminosilane reagents is that aminopropyl-triethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxy silane, diethylenetriamine base propyl trimethoxy silicane or other contain amino silane reagent, the volume of the organic solvent of using during backflow be aminosilane reagents 10-40 doubly.
The concentration of the aqueous solution of described metal precursor is at 0.0001-1molL
-1
The predecessor of described gold comprises the aqueous solution of other organic coordination compounds of gold chloride, auribromohydric acid, chloroaurate, bromaurate or gold, and the predecessor of nickel comprises nickel chloride, nickel nitrate, nickelous sulfate, the aqueous solution of other organic complexs of nickel acetate or nickel.
The w/v of carrier and the metal precursor aqueous solution is 1: 10-1: 100.
The present invention has following advantage:
1. metal precursor and the reducing agent of the present invention's employing are all cheap and easy to get.
2. the inventory of the actual loading of metal and molar ratio and metal and rate of charge approach among the present invention, save metal consumption.
3. two kinds of metals that will be difficult for forming the body that dissolves each other among the present invention are made Nanoalloy.
4. the golden nickel nano particle that makes among the present invention has high thermal stability, and high degree of dispersion is on carrier.Behind 500 ℃ of air roasting 6h and 550 ℃ of processing of hydrogen 1h, the average grain diameter of golden nickel alloy nano particle is about 3.5nm, and the particle size narrowly distributing.
5. oxidation has very high catalytic activity to the golden nickel alloy nano particle among the present invention to CO, and the active catalytic activity that is higher than the monometallic gold.Consist of CO at unstripped gas: O
2: He=1: 1: 98 (volume ratio), gas space velocity are 40000 mLg
Cat-1h
-1Under the condition, when nickel gold mol ratio less than 1 the time, since the CO conversion ratio of 40 ℃ of golden nickel alloy nanocatalysts near 100%.
6. for other catalytic reactions of nm of gold and nano nickel, for example selective hydrogenation reaction has potential application.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of catalyst A 1, A2, A3, A4 and A5.
Fig. 2 is that catalyst A 1 is at the HAADF in different disposal stage electromicroscopic photograph and particle diameter statistical Butut.
Fig. 3 is projection electron microscope (TEM) and the HAADF electromicroscopic photograph of catalyst A 2.
Fig. 4 is that the high resolution electron microscopy photo of interplanar distance and the electron spectrum (EDS) of the single particle of catalyst A 1 analyzed.
Fig. 5 is that the electron spectrum (EDS) of the single particle of catalyst A 2 is analyzed.
Fig. 6 is Ni-K limit and the Au L of catalyst A 1 in the different disposal stage
IIILimit k
3Fourier transformation EXAFS characterization result.
Fig. 7 is the temperature variant activity of the carbon monoxide of catalyst A 1, A2, A3, A4 and A5.
The specific embodiment
According to document (Zhao, D.Y.; Huo, Q.S.; Feng, J.L.; Chmelka, B.F.; Stucky, G.D.Journal of the American Chemical Society 1998,120, the SBA-15 that enriches hydroxyl is contained on the synthetic method preparation surface in 6024-6036).Under 40 ℃ of conditions, 2g P123 is dissolved in the aqueous solution of 15g water and 60g hydrochloric acid (2M), fully after the dissolving, in situation about constantly stirring, add tetraethoxysilance 4.25g, continue to stir 24h, put into 100 ℃ of crystallization 48h of reactor, filter, drying obtains white powder SBA-15.
8g SBA-15 is put into dry there-necked flask, 100 ℃ of oven dry of baking oven 2 hours, add the 400mL absolute ethyl alcohol after being down to room temperature, amino triethoxysilane (the 3-aminopropyltriethoxysilane of rear adding 21.2mL stirs, 99%, Acros Organics) 80 ℃ were refluxed 24 hours, then filtered solids of sedimentation and were washed till with the copper nitrate check without blue flocculent deposit with absolute ethyl alcohol.Solid was put into 60 ℃ of oven for drying 6 hours afterwards, obtained the carrier S BA-15-APTES of amino functional.
With 8g SiO
2Put into dry there-necked flask, 100 ℃ of oven dry of baking oven 2 hours, add the 400mL absolute ethyl alcohol after being down to room temperature, amino triethoxysilane (the 3-aminopropyltriethoxysilane of rear adding 21.2mL stirs, 99%, Acros Organics) 80 ℃ were refluxed 24 hours, then filtered solids of sedimentation and were washed till with the copper nitrate check without blue flocculent deposit with absolute ethyl alcohol.Solid was put into 60 ℃ of oven for drying 6 hours afterwards, obtained the carrier S iO of amino functional
2-APTES.
Add 16mL deionized water and the aqueous solution of chloraurate 6mL that contains golden 9.56mg/mL in the 100mL beaker, rear adding 1.1118g SiO at room temperature stirs
2-APTES continued to stir after 30 minutes, filtered and washed with the 1000mL deionized water.The solid that obtains is re-dispersed in the 100mL beaker that the 11mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 11mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water.The solid that obtains is distributed to 11mL deionized water and 0.2540g Ni (NO is housed
3)
26H
2In the beaker of O, at room temperature drip while stirring 0.2M tert-butyl group ammonia borine aqueous solution 30mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water, at room temperature put into 80 ℃ of oven dryings after the drying 12 hours, the catalyst that obtain this moment is denoted as A1-dry, its electromicroscopic photograph is shown in Fig. 2 a, and particle is dispersed in carrier S iO
2On, particle size distribution is narrow, average grain diameter 2.78nm.Catalyst A 1-dry is risen to 500 ℃ with the programming rate of 1.5 ℃/min, remained on afterwards in 500 ℃ the air roasting 6 hours, the catalyst meter that obtains after the roasting is made A1-cal, and its electromicroscopic photograph is shown in Fig. 2 b, and particle is dispersed in carrier S iO
2On, particle size distribution is narrow, average grain diameter 3.36nm.Catalyst A 1-cal is risen to 550 ℃ with the programming rate of 8 ℃/min, remained on afterwards in 550 ℃ the hydrogen reduction 1 hour, obtain catalyst after the reduction and be denoted as A1, its electromicroscopic photograph is shown in Fig. 2 c, and particle is dispersed in carrier S iO
2On, particle size distribution is narrow, average grain diameter 3.35nm.Catalyst A 1 is risen to 300 ℃ with the programming rate of 8 ℃/min, remain on afterwards 300 ℃ oxygenous 5% O
2Oxidation is 1 hour in the/He gaseous mixture, obtains catalyst after the oxidation and is denoted as A1-O
2, its electromicroscopic photograph is shown in Fig. 2 d, and particle is dispersed in carrier S iO
2On, particle size distribution is narrow, average grain diameter 3.35nm.Can find out, the Au-Ni alloy nano particle that a process for preparing not only can be on carrier high degree of dispersion, and narrow diameter distribution also has high thermal stability, after no matter being high temperature reduction processing or high temperature oxidation process, the particle diameter of nano particle is also without obviously growing up.
Add 17.5mL deionized water and the aqueous solution of chloraurate 2.5mL that contains golden 19.12mg/mL in the 100mL beaker, rear adding 0.956g SiO at room temperature stirs
2-APTES continued to stir after 30 minutes, filtered and washed with the 1000ml deionized water.The solid that obtains is re-dispersed in the 100mL beaker that the 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water.The solid that obtains is distributed to the Ni (NO that 5mL deionized water and 0.05M are housed
3)
2In the beaker of aqueous solution 4.85mL, at room temperature drip while stirring 0.2M tert-butyl group ammonia borine aqueous solution 8mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water, at room temperature put into 80 ℃ of oven dryings after the drying 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour obtain catalyst A 2, and particle is evenly distributed in SiO
2On, particle size distribution is narrow, and average grain diameter 3.5nm sees Fig. 3.
Add 15mL deionized water and the aqueous solution of chloraurate 5mL that contains golden 9.56mg/mL in the 100mL beaker, rear adding 0.956g SiO at room temperature stirs
2-APTES continued to stir after 30 minutes, filtered and washed with the 1000ml deionized water.The solid that obtains is re-dispersed in the 100mL beaker that the 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water.The solid that obtains is distributed to the Ni (NO that 8.5mL deionized water and 0.05M are housed
3)
2In the beaker of aqueous solution 1.62mL, at room temperature drip while stirring 0.2M tert-butyl group ammonia borine aqueous solution 5.5mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water, at room temperature put into 80 ℃ of oven dryings after the drying 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour obtain catalyst A 3.
Add 15mL deionized water and the aqueous solution of chloraurate 5mL that contains golden 9.56mg/mL in the 100mL beaker, rear adding 0.956g SiO at room temperature stirs
2-APTES continued to stir after 30 minutes, filtered and washed with the 1000ml deionized water.The solid that obtains is re-dispersed in the 100mL beaker that the 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water.The solid that obtains is distributed to the Ni (NO that 9mL deionized water and 0.05M are housed
3)
2In the beaker of aqueous solution 1.21mL, at room temperature drip while stirring 0.2M tert-butyl group ammonia borine aqueous solution 4mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water, at room temperature put into 80 ℃ of oven dryings after the drying 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour obtain catalyst A 4.
Add 15mL deionized water and the aqueous solution of chloraurate 5mL that contains golden 9.56mg/mL in the 100mL beaker, rear adding 0.956g SiO at room temperature stirs
2-APTES continued to stir after 30 minutes, filtered and washed with the 1000ml deionized water.The solid that obtains is re-dispersed in the 100mL beaker that the 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water.The solid that obtains is distributed to the Ni (NO that 9.5mL deionized water and 0.05M are housed
3)
2In the beaker of aqueous solution 0.48mL, at room temperature drip while stirring 0.2M tert-butyl group ammonia borine aqueous solution 4mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water, at room temperature put into 80 ℃ of oven dryings after the drying 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour obtain catalyst A 5.
Adopt X-ray diffraction to characterize catalyst A 1, A2, A3, A4 and A5, the obvious broadening of metal diffraction maximum and between monometallic Au and monometallic Ni is seen Fig. 1.This explanation has formed the AuNi alloy, and particle size homogeneous and particle diameter are little.
Embodiment 9
Adopt high resolution electron microscopy to obtain the spacing of lattice of nano particle on the catalyst A 1, spacing of lattice illustrates to have formed the AuNi alloy between monometallic Au and monometallic Ni, sees Fig. 4 a; Single nano particle on the catalyst A 1 has been carried out the element energy spectrum analysis, found that most of particles contain Au and two kinds of elements of Ni simultaneously, illustrate that nano particle is bimetal nano particles, sees Fig. 4 b.
To the element energy spectrum analysis of the single particle on the catalyst A 2, find to contain simultaneously Au and two kinds of elements of Ni on the particle, illustrate to have formed bimetal nano particles, see Fig. 5.
Embodiment 11
The characterization result that adopts the EXAFS technology that catalyst A 1-cal has been carried out in-situ characterization: catalyst A 1-cal is seen a series among the curve a and table 1 among Fig. 6; Catalyst A 1-cal is carried out 500 ℃ of hydrogen reduction 1 hour, be down to characterization result after the room temperature and see the b series among the curve b and table 1 among Fig. 6; Again catalyst A 1 is being contained 5%O
2O
2Processed 1 hour for 300 ℃ in the-He gaseous mixture, characterize after being down to room temperature, the results are shown in Figure the c series among the curve c and table 1 in 6.Can find out from the analysis result of the EXAFS of Fig. 6 and table 1, only have after catalyst A 1-cal is through high-temperature hydrogen reduction processing, shown in b series, a large amount of Au-Ni chemical bonds has just appearred, illustrate in the catalyst at this moment to have formed the Au-Ni alloy, illustrate that it is the committed step that forms the Au-Ni alloy that the high-temperature hydrogen reduction is processed.
Embodiment 12
Consist of CO at unstripped gas: O
2: He=1: 1: 98 (volume ratio), gas space velocity are 40000 mLg
Cat-1h
-1Under the condition, estimated the reactivity variation with temperature, found when temperature is higher than 40 ℃, the activity of the AuNi alloy catalyst all catalytic activity than monometallic gold is high; Since the carbon monoxide conversion ratio of 40 ℃ of catalyst A 3 and A4 near 100%.The results are shown in Figure 7.As seen, thus utilize this preparation method to form the activity that alloy improves the catalysis CO oxidation of monometallic Au by Ni and Au.
Embodiment 13
Adopt the ICP technology that the content that catalyst A 1, A2, A3, A4 and A5 carry out metal A u and Ni is measured, and its inventory with Kaolinite Preparation of Catalyst is compared, it is approaching to find both, the results are shown in Table 2.Utilize method to reach its actual loading of accurate control by the inventory of control carrying metal, not only can save the consumption of metal, and the effective preparation method of accurate design catalyst is provided for Catalysis Principles research.
Table 1 is that catalyst A 1 is Ni, the O in different disposal stage and ligancy (CN) and the bond distance (R) of Au.
| Ni-O | Ni-Ni | Ni-Au | Au-Au | Au-Ni | |
| CN a | 4.93 | 9.42 | 0.33 | 9.24 | 0.38 |
| R a | 2.06 | 2.99 | 2.69 | 2.83 | 2.69 |
| CN b | 2.68 | 1.27 | 2.44 | 4.96 | 3.36 |
| R b | 2.06 | 2.48 | 2.62 | 2.78 | 2.62 |
| CN c | 4.76 | 7.96 | - | 9.74 | - |
| R c | 2.05 | 2.98 | - | 2.82 | - |
Table 2 is actual loading and the inventory of the upper metal of catalyst A 1, A2, A3, A4 and A5.
Comparative Examples 1
Ni (the NO that adds 5mL deionized water and 0.05M in the 50mL beaker
3)
2Aqueous solution 4.85mL adds 0.956g SiO again
2-APTES makes it to scatter, and at room temperature drips while stirring 0.2M tert-butyl group ammonia borine aqueous solution 8mL, continues to stir after 30 minutes and filters, and adds NaBH in filtrate
4Rear filtrate is the browning look immediately, illustrates to have the nickel that is not reduced in a large number, and in the situation that does not have golden nanometer particle to exist, weak reductant can not be with the reduction of nickel;
Comparative Examples 2
Add 17.5mL deionized water and the aqueous solution of chloraurate 2.5mL that contains golden 19.12mg/mL in the 100mL beaker, rear adding 0.956g SiO at room temperature stirs
2-APTES continued to stir after 30 minutes, filtered and washed with the 1000ml deionized water.The solid that obtains is re-dispersed in the 100mL beaker that the 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water.The solid that obtains is distributed to the Ni (NO that 5mL deionized water and 0.05M are housed
3)
2In the beaker of aqueous solution 4.85mL, at room temperature drip while stirring 0.2M sodium borohydride aqueous solution 22mL, continue to stir and filter after 15 minutes and wash with the 1000mL deionized water, at room temperature put into 80 ℃ of oven dryings after the drying 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour obtain catalyst A 6.Be with examples of implementation 4 differences, adopt strong reductant sodium borohydride reduction nickel at this, because the reduction rate of nickel is too fast, cause forming a large amount of monometallic nickel particles, through the golden nickel alloy particle that only has small part to form behind the roasting reduction.
Claims (8)
1. the preparation method of a loaded golden nickel alloy nano particle is characterized in that:
The group that at first grafting can complexation of metal ions on the carrier of rich surface hydroxyl functional group, make golden nanometer particle by the complexing gold and with its reduction again, again take golden nanometer particle as nuclear absorbed Ni ion and with the reduction of weak reductant catalytic nickel, through obtaining golden nickel alloy nano particle after air roasting and the hydrogen high-temperature process, total weight metal loading of catalyst is 0.1-10%, and the mol ratio of nickel and gold is at 0.001-5.
2. according to preparation method claimed in claim 1, it is characterized in that: the group of energy complexation of metal ions is-NH
2,-SH ,-NH-or-N=C-R; Described weak reductant is organo-borane.
3. according to catalyst claimed in claim 1, it is characterized in that:
Specific operation process is as follows,
1) with the carrier of rich surface hydroxyl functional group according to the ratio of the corresponding 1-4ml aminosilane reagents of 1g carrier under the organic solvent condition 60-100 ℃ backflow 2-48 hour, filter and use organic solvent washing, dried 1-6 hour for 40-80 ℃, obtain the carrier of surface amination;
2) in the time of 0-40 ℃, the aqueous solution that carrier is joined the predecessor of solubility gold carries out complexing, after the washing, adds the strong reductant reduction after filtration, after filtration after the washing; With containing in the predecessor aqueous solution that golden carrier is distributed to soluble nickel of obtaining, the molar ratio of nickel and gold is at 0.001-5, add simultaneously the weak reductant reduction, after filtration after the washing, with pressed powder through drying at room temperature, again through 60-120 ℃ of oven dry, 350-600 ℃ of air roasting, 500-700 ℃ of hydrogen reducing obtains loaded golden nickel alloy nano particle;
Described 350-600 ℃ of air roasting process is: the material after will drying rises to 350-600 ℃ with the programming rate of 1-10 ℃/min, and remains in 350-600 ℃ the air roasting 3-10 hour;
Described 500-700 ℃ of hydrogen reducing process is: the material behind the air roasting is risen to 500-700 ℃ with the programming rate of 1-20 ℃/min, and remained in 500-700 ℃ the hydrogen reduction 1-5 hour;
Described strong reductant is hydrazine hydrate or sodium borohydride; Described weak reductant is organo-borane.
4. it is characterized in that according to claim 2 or the preparation method of 3 described catalyst:
Described organo-borane is the tert-butylamine borine.
5. the preparation method of catalyst according to claim 1 and 2 is characterized in that:
The carrier of described rich surface hydroxyl functional group contains silica, titanium oxide, aluminium oxide, molecular screen material or the material with carbon element of hydroxyl functional group for the surface;
Strong reductant or weak reductant add with the form of the aqueous solution, and the concentration of aqueous solution of reducing agent is at 0.001-5molL
-1
6. according to preparation method claimed in claim 2, it is characterized in that: described organic solvent is one or more in benzene, toluene, ethanol, the cyclohexane;
Described aminosilane reagents is aminopropyl-triethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxy silane or diethylenetriamine base propyl trimethoxy silicane, and the volume of the organic solvent of using during backflow is 10-40 times of aminosilane reagents.
7. according to preparation method claimed in claim 3, it is characterized in that:
The predecessor of described solubility gold comprises the aqueous solution of other organic coordination compounds of gold chloride, auribromohydric acid, chloroaurate, bromaurate or gold, the predecessor of soluble nickel comprises nickel chloride, nickel nitrate, nickelous sulfate, the aqueous solution of other organic complexs of nickel acetate or nickel.
8. according to preparation method claimed in claim 3, it is characterized in that:
The concentration of the aqueous solution of the predecessor of gold or nickel is at 0.0001-1molL
-1
The w/v of the predecessor aqueous solution of carrier and gold or nickel is 1: 10-1: 100.
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| CN107570152A (en) * | 2017-08-17 | 2018-01-12 | 孟庆桓 | A kind of catalyst and hydrotreating method for high calcium content heavy crude oil hydrocracking |
| CN108014789A (en) * | 2017-12-06 | 2018-05-11 | 福州大学 | A kind of loaded catalyst for the poly- cyclohexyl. vinyl of polystyrene Hydrogenation and preparation method thereof |
| CN111185168A (en) * | 2020-01-14 | 2020-05-22 | 上海华谊（集团）公司 | Nano gold catalyst, preparation and application thereof |
| CN111821999A (en) * | 2019-04-23 | 2020-10-27 | 中南林业科技大学 | Method for treating nitroaromatic substances by using modified carbon black loaded nickel-gold bimetallic nano-catalyst |
| CN115739092A (en) * | 2021-09-03 | 2023-03-07 | 广东工业大学 | High-activity metallic nickel supported catalyst and preparation method and application thereof |
| CN117399011A (en) * | 2023-10-10 | 2024-01-16 | 天水师范学院 | Preparation method of nickel-copper catalytic material for hydrocarbon saturated hydrogenation |
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| CN107570152A (en) * | 2017-08-17 | 2018-01-12 | 孟庆桓 | A kind of catalyst and hydrotreating method for high calcium content heavy crude oil hydrocracking |
| CN108014789A (en) * | 2017-12-06 | 2018-05-11 | 福州大学 | A kind of loaded catalyst for the poly- cyclohexyl. vinyl of polystyrene Hydrogenation and preparation method thereof |
| CN111821999A (en) * | 2019-04-23 | 2020-10-27 | 中南林业科技大学 | Method for treating nitroaromatic substances by using modified carbon black loaded nickel-gold bimetallic nano-catalyst |
| CN111821999B (en) * | 2019-04-23 | 2023-05-23 | 中南林业科技大学 | Method for treating nitroaromatic hydrocarbon substances by using modified carbon black loaded nickel-gold bimetallic nano catalyst |
| CN111185168A (en) * | 2020-01-14 | 2020-05-22 | 上海华谊（集团）公司 | Nano gold catalyst, preparation and application thereof |
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| CN115739092A (en) * | 2021-09-03 | 2023-03-07 | 广东工业大学 | High-activity metallic nickel supported catalyst and preparation method and application thereof |
| CN117399011A (en) * | 2023-10-10 | 2024-01-16 | 天水师范学院 | Preparation method of nickel-copper catalytic material for hydrocarbon saturated hydrogenation |
| CN117399011B (en) * | 2023-10-10 | 2024-05-07 | 天水师范学院 | Preparation method of nickel-copper catalytic material for hydrocarbon saturated hydrogenation |
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