CN102909034B - Preparation of supported gold-nickel alloy nanocatalyst - Google Patents
Preparation of supported gold-nickel alloy nanocatalyst Download PDFInfo
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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 be better than the activity and selectivity of single-metal reforming catalyst more and more noticeable because it shows in a lot of reactions for alloy catalyst.Since the preparation method (JP60238148 and JP0194945) of the clear supported nano Au catalyst of the human hairs such as Japanese Haruta, nano-Au catalyst is found in the reactions such as the selective hydrogenation of selective oxidation, propylene ring oxidation reaction and the nitryl aromatic alkene of CO low temperature oxidation, alcohol and shows peculiar catalytic performance.Raney nickel is in a lot of hydrogenation reactions, as the reaction table such as aromatic hydrogenation, solvent oil hydrogenation reveals high activity (CN1415413).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 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 golden inorganic salt solution preparing, gold particle is introduced among duct, through the mist reduction of hydrogen and nitrogen, make size uniform, the significant nm of gold of quantum effect is carried on the composite among nano-pore duct.But whether the state of not mentioning Au and Ni is alloy state.
CN1037072C has introduced a kind of preparation of particle Ni-Pd alloy catalyst, in vacuum chamber, nickel plate is put on anode, palladium thin slice press with nickel plate on, utilize electric arc that nickle atom and palladium atom are collided with each other, preparation nanometer NiPd alloy ultro-micro partical catalyst.
In sum, also there is no at present the report about the preparation method of loaded AuNi alloy nano particle.Because the fusing point of Au is lower, in the time of high-temperature process, easily assemble, and Ni belongs to refractory metal, not only can improve the stability of Au by forming AuNi alloy, and can reduce the cost of catalyst; In addition, after formation alloy, may in some reactions, can show and be better than the active or selective of single-metal reforming catalyst; And AuNi sees and is not easy to form alloy from phasor.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, again by complexing gold and its reduction is made to golden nanometer particle, the reduction of catalytic nickel take golden nanometer particle as core absorbed Ni ion and together with weak reductant again, after air roasting and hydrogen high-temperature process, obtain golden nickel alloy nano particle, in the catalyst making, the actual loading of gold and nickel and molar ratio and inventory and rate of charge approach, total weight metal loading of catalyst is 0.1-10%, nickel and golden mol ratio are at 0.001-5.Gold nickel alloy nano particle high degree of dispersion, on carrier, and has high thermal stability, and after air roasting and hydrogen reducing, the average grain diameter of particle is 3.5nm, and narrow size distribution.This catalyst shows the high activity higher than monometallic Au catalyst in reaction of carbon monoxide.
Concrete operations condition is as follows:
1) surface is contained to the carrier that enriches hydroxyl according to ratio 60-100 ℃ of backflow 2-48 hour under organic solvent condition of the corresponding 1-4ml aminosilane reagents of 1g carrier, filter and use organic solvent washing, dry 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 to golden predecessor carries out complexing, after filtration after washing, add appropriate strong reductant reduction, after filtration after washing, by being distributed in the predecessor aqueous solution of nickel containing golden carrier of obtaining, nickel and golden ratio are at 0.001-5, add the reduction of appropriate weak reductant simultaneously, after filtration after washing, by 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 drying is risen to 350-600 ℃ with the programming rate of 1-10 ℃/min, and remain on roasting 3-10 hour in the air of 350-600 ℃;
Described 500-700 ℃ of hydrogen reducing process is: the material after air roasting is risen to 500-700 ℃ with the programming rate of 1-20 ℃/min, and remain on and in the hydrogen of 500-700 ℃, reduce 1-5 hour;
Described strong reductant is hydrazine hydrate or sodium borohydride.
Described weak reductant is organo-borane, for example, and tert-butylamine borine.
The concentration of aqueous solution of reducing agent is at 0.001-5molL
-1
The present invention carries out the predecessor reduction process of the complexing of nickel ion and nickel simultaneously, and does not carry out washing and filtering operation after nickel ion complexing, makes actual loading and the inventory of nickel suitable; Simultaneously reduction process adsorb take golden nanometer particle as core and with weak reductant together catalytic nickel reduce in gold surface, after roasting and hydrogen reducing, make nickel and gold be completed into alloy;
In the situation that there is no golden nanometer particle, weak reductant can not reduce nickel; And in the time that this adopts strong reductant to reduce to nickel, the carrier surface that the nickel of reduction has most of physical absorption to exist in non-golden nanometer particle, only has small part chemisorbed in golden nanometer particle surface, after roasting and hydrogen reducing, there is a large amount of nickel simple substance to exist, and only have a small amount of nickel and gold to form alloy.
Described organic solvent is one or more in benzene, toluene, ethanol, cyclohexane, described aminosilane reagents be aminopropyl-triethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxy silane, diethylenetriamine base propyl trimethoxy silicane or other containing amino silane reagent, the volume of the organic solvent of using when backflow be aminosilane reagents 10-40 doubly.
The concentration of the aqueous solution of described metal precursor is at 0.0001-1molL
-1
Described golden predecessor 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.
Tool of the present invention has the following advantages:
1. the present invention adopts metal precursor and reducing agent are all cheap and easy to get.
2. in the present invention, the actual loading of metal and the inventory of molar ratio and metal and rate of charge approach, and save metal consumption.
3. in the present invention, difficult two kinds of metals that form the body that dissolves each other are made to Nanoalloy.
4. the golden nickel nano particle making in the present invention has high thermal stability, and high degree of dispersion is on carrier.After 500 ℃ of air roasting 6h and 550 ℃ of processing 1h of hydrogen, the average grain diameter of golden nickel alloy nano particle is 3.5nm left and right, and particle size narrowly distributing.
5. to CO, oxidation has very high catalytic activity to the golden nickel alloy nano particle in the present invention, and the active catalytic activity higher than monometallic gold.Consist of CO at unstripped gas: O
2: He=1: 1: 98 (volume ratio), gas space velocity is 40000 mLg
cat-1h
-1under condition, in the time that nickel gold mol ratio is less than 1, approach 100% since the CO conversion ratio of 40 ℃ of golden nickel alloy nanocatalysts.
6. for other catalytic reactions of nm of gold and nano nickel, for example selective hydrogenation reaction has potential application.
Accompanying drawing explanation
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 high resolution electron microscopy photo and the electron spectrum (EDS) of the interplanar distance 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 1998,120,6024-6036) in synthetic method preparation surface contain the SBA-15 that enriches hydroxyl.Under 40 ℃ of conditions, 2g P123 is dissolved in the aqueous solution of 15g water and 60g hydrochloric acid (2M), after dissolving completely, in the situation that constantly stirring, add tetraethoxysilance 4.25g, continue to stir 24h, put into 100 ℃ of crystallization 48h of reactor, filter, dry, obtain white powder SBA-15.
8g SBA-15 is put into dry there-necked flask, 100 ℃ of oven dry of baking oven 2 hours, after being down to room temperature, add 400mL absolute ethyl alcohol, after stirring, add the amino triethoxysilane (3-aminopropyltriethoxysilane of 21.2mL, 99%, Acros Organics) 80 ℃ reflux 24 hours, then filter solids of sedimentation and be washed till and check without blue flocculent deposit with copper nitrate with absolute ethyl alcohol.Solid is put into 60 ℃ of oven for drying 6 hours afterwards, obtained the carrier S BA-15-APTES of amino functional.
By 8g SiO
2put into dry there-necked flask, 100 ℃ of oven dry of baking oven 2 hours, after being down to room temperature, add 400mL absolute ethyl alcohol, after stirring, add the amino triethoxysilane (3-aminopropyltriethoxysilane of 21.2mL, 99%, Acros Organics) 80 ℃ reflux 24 hours, then filter solids of sedimentation and be washed till and check without blue flocculent deposit with copper nitrate with absolute ethyl alcohol.Solid is put into 60 ℃ of oven for drying 6 hours afterwards, obtained the carrier S iO of amino functional
2-APTES.
In 100mL beaker, add 16mL deionized water and the aqueous solution of chloraurate 6mL that contains golden 9.56mg/mL, after at room temperature stirring, add 1.1118g SiO
2-APTES continues to stir after 30 minutes, filters and use the washing of 1000mL deionized water.The solid obtaining is re-dispersed in the 100mL beaker that 11mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 11mL, continue stirring and after 15 minutes, filter and use the washing of 1000mL deionized water.The solid obtaining 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 stirring and after 15 minutes, filter and use the washing of 1000mL deionized water, after being at room temperature dried, put into 80 ℃ of oven dryings 12 hours, the catalyst now obtaining is denoted as A1-dry, as shown in Figure 2 a, particle is dispersed in carrier S iO to its electromicroscopic photograph
2upper, 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, remain on afterwards in the air of 500 ℃ roasting 6 hours, the catalyst meter obtaining after roasting is made A1-cal, and as shown in Figure 2 b, particle is dispersed in carrier S iO to its electromicroscopic photograph
2upper, 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, remain on afterwards in the hydrogen of 550 ℃ and reduce 1 hour, obtain catalyst and be denoted as A1 after reduction, as shown in Figure 2 c, particle is dispersed in carrier S iO to its electromicroscopic photograph
2upper, 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 oxygenous 5% the O of 300 ℃
2in/He gaseous mixture, be oxidized 1 hour, after oxidation, obtain catalyst and be denoted as A1-O
2, as shown in Figure 2 d, particle is dispersed in carrier S iO to its electromicroscopic photograph
2upper, particle size distribution is narrow, average grain diameter 3.35nm.Can find out, the Au-Ni alloy nano particle 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.
In 100mL beaker, add 17.5mL deionized water and the aqueous solution of chloraurate 2.5mL that contains golden 19.12mg/mL, after at room temperature stirring, add 0.956g SiO
2-APTES continues to stir after 30 minutes, filters and use the washing of 1000ml deionized water.The solid obtaining is re-dispersed in the 100mL beaker that 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue stirring and after 15 minutes, filter and use the washing of 1000mL deionized water.The solid obtaining 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 stirring and after 15 minutes, filter and use the washing of 1000mL deionized water, after being at room temperature dried, put into 80 ℃ of oven dryings 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
2upper, particle size distribution is narrow, and average grain diameter 3.5nm is shown in Fig. 3.
In 100mL beaker, add 15mL deionized water and the aqueous solution of chloraurate 5mL that contains golden 9.56mg/mL, after at room temperature stirring, add 0.956g SiO
2-APTES continues to stir after 30 minutes, filters and use the washing of 1000ml deionized water.The solid obtaining is re-dispersed in the 100mL beaker that 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue stirring and after 15 minutes, filter and use the washing of 1000mL deionized water.The solid obtaining 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 stirring and after 15 minutes, filter and use the washing of 1000mL deionized water, after being at room temperature dried, put into 80 ℃ of oven dryings 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour, obtain catalyst A 3.
In 100mL beaker, add 15mL deionized water and the aqueous solution of chloraurate 5mL that contains golden 9.56mg/mL, after at room temperature stirring, add 0.956g SiO
2-APTES continues to stir after 30 minutes, filters and use the washing of 1000ml deionized water.The solid obtaining is re-dispersed in the 100mL beaker that 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue stirring and after 15 minutes, filter and use the washing of 1000mL deionized water.The solid obtaining 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 stirring and after 15 minutes, filter and use the washing of 1000mL deionized water, after being at room temperature dried, put into 80 ℃ of oven dryings 12 hours, 500 ℃ of roastings of air 6 hours, 550 ℃ of processing of hydrogen 1 hour, obtain catalyst A 4.
In 100mL beaker, add 15mL deionized water and the aqueous solution of chloraurate 5mL that contains golden 9.56mg/mL, after at room temperature stirring, add 0.956g SiO
2-APTES continues to stir after 30 minutes, filters and use the washing of 1000ml deionized water.The solid obtaining is re-dispersed in the 100mL beaker that 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue stirring and after 15 minutes, filter and use the washing of 1000mL deionized water.The solid obtaining 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 stirring and after 15 minutes, filter and use the washing of 1000mL deionized water, after being at room temperature dried, put into 80 ℃ of oven dryings 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 shown in Fig. 1.This explanation has formed 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 in catalyst A 1, spacing of lattice between monometallic Au and monometallic Ni, illustrates and has formed AuNi alloy, sees Fig. 4 a; Single nano particle in catalyst A 1 is carried out to element energy spectrum analysis, found that most of particles contain Au and two kinds of elements of Ni, illustrate that nano particle is bimetal nano particles, sees Fig. 4 b simultaneously.
To the element energy spectrum analysis of the single particle in catalyst A 2, find to contain Au and two kinds of elements of Ni on a particle simultaneously, illustrate and formed bimetal nano particles, see Fig. 5.
Embodiment 11
The characterization result that adopts EXAFS technology to carry out in-situ characterization: catalyst A 1-cal to catalyst A 1-cal is shown in a series in curve a and table 1 in Fig. 6; Catalyst A 1-cal is carried out to 500 ℃ of hydrogen reduction 1 hour, be down to characterization result after room temperature and see the b series in curve b and table 1 in Fig. 6; Again catalyst A 1 is being contained to 5%O
2o
2in-He gaseous mixture, process 1 hour for 300 ℃, characterize after being down to room temperature, the results are shown in Figure the c series in 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 when catalyst A 1-cal is after high-temperature hydrogen reduction processing, as shown in b series, just there is a large amount of Au-Ni chemical bonds, illustrate in catalyst now and formed Au-Ni alloy, illustrate that it is the committed step that forms Au-Ni alloy that 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 is 40000 mLg
cat-1h
-1under condition, evaluate reactivity variation with temperature, found that the activity of AuNi alloy catalyst is all high than the catalytic activity of monometallic gold when temperature is during higher than 40 ℃; Approach 100% since the carbon monoxide conversion ratio of 40 ℃ of catalyst A 3 and A4.The results are shown in Figure 7.Visible, improve the activity of the catalysis CO oxidation of monometallic Au thereby utilize this preparation method to form alloy by Ni and Au.
Embodiment 13
The content that adopts ICP technology to carry out metal A u and Ni to catalyst A 1, A2, A3, A4 and A5 is measured, and itself and the inventory of Kaolinite Preparation of Catalyst are compared, and finds both approaching, the results are shown in Table 2.Utilize method to reach its actual loading of accurate control by controlling the inventory of carrying metal, not only can save the consumption of metal, and provide the effective preparation method of accurate design catalyst for Catalysis Principles research.
Table 1 is that catalyst A 1 is Ni, the O in different disposal stage and the ligancy (CN) of Au and bond distance (R).
| 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 example 1
To the Ni (NO that adds 5mL deionized water and 0.05M in 50mL beaker
3)
2aqueous solution 4.85mL, then add 0.956g SiO
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 in filtrate, adds NaBH
4rear filtrate is browning look immediately, illustrates and has the nickel not being reduced in a large number, and in the situation that there is no golden nanometer particle, weak reductant can not be by the reduction of nickel;
Comparative example 2
In 100mL beaker, add 17.5mL deionized water and the aqueous solution of chloraurate 2.5mL that contains golden 19.12mg/mL, after at room temperature stirring, add 0.956g SiO
2-APTES continues to stir after 30 minutes, filters and use the washing of 1000ml deionized water.The solid obtaining is re-dispersed in the 100mL beaker that 10mL deionized water is housed, at room temperature drips while stirring 0.2M sodium borohydride aqueous solution 9mL, continue stirring and after 15 minutes, filter and use the washing of 1000mL deionized water.The solid obtaining 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 stirring and after 15 minutes, filter and use the washing of 1000mL deionized water, after being at room temperature dried, put into 80 ℃ of oven dryings 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, the golden nickel alloy particle that only has small part to form after roasting reduction.
Claims (8)
1. a preparation method for loaded golden nickel alloy nano particle, is characterized in that:
First the group of grafting energy complexation of metal ions on the carrier of rich surface hydroxyl functional group, again by complexing gold and its reduction is made to golden nanometer particle, the reduction of catalytic nickel take golden nanometer particle as core absorbed Ni ion and together with weak reductant again, after air roasting and hydrogen high-temperature process, obtain golden nickel alloy nano particle, total weight metal loading of catalyst is 0.1-10%, and nickel and golden mol ratio are at 0.001-5; Described weak reductant is organo-borane.
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.
3. according to preparation method claimed in claim 1, it is characterized in that:
Specific operation process is as follows,
1) by the carrier of rich surface hydroxyl functional group according to ratio 60-100 ℃ of backflow 2-48 hour under organic solvent condition of the corresponding 1-4ml aminosilane reagents of 1g carrier, filter and use organic solvent washing, dry 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 to the predecessor of solubility gold carries out complexing, after washing, adds strong reductant reduction after filtration, after filtration after washing; By being distributed in the predecessor aqueous solution of soluble nickel containing golden carrier of obtaining, nickel and golden molar ratio are at 0.001-5, add weak reductant reduction simultaneously, after filtration after washing, by pressed powder through drying at room temperature, then 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 drying is risen to 350-600 ℃ with the programming rate of 1-10 ℃/min, and remain on roasting 3-10 hour in the air of 350-600 ℃;
Described 500-700 ℃ of hydrogen reducing process is: the material after air roasting is risen to 500-700 ℃ with the programming rate of 1-20 ℃/min, and remain on and in the hydrogen of 500-700 ℃, reduce 1-5 hour;
Described strong reductant is hydrazine hydrate or sodium borohydride; Described weak reductant is organo-borane.
4. according to the preparation method described in claim 2 or 3, it is characterized in that:
Described organo-borane is tert-butylamine borine.
5. preparation method according to claim 1 and 2, is characterized in that:
The carrier of described rich surface hydroxyl functional group is silica, titanium oxide, aluminium oxide, molecular screen material or the material with carbon element that hydroxyl functional group is contained on 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 3, it is characterized in that: described organic solvent is one or more in benzene, toluene, ethanol, 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 when 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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