CN104874404A - Magnetic graphene-based platinum-nickel bimetallic catalyst and preparation method of magnetic graphene-based platinum-nickel bimetallic catalyst - Google Patents
Magnetic graphene-based platinum-nickel bimetallic catalyst and preparation method of magnetic graphene-based platinum-nickel bimetallic catalyst Download PDFInfo
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Abstract
The invention relates to a magnetic graphene-based platinum-nickel bimetallic catalyst and a preparation method of the magnetic graphene-based platinum-nickel bimetallic catalyst. Platinum-nickel alloy type bimetallic nanoparticles with the particle size being 10-20nm are loaded on a graphene carrier, the saturation magnetization of the catalyst at 15-35 DEG C is 8-13emu/g, and the bimetallic catalyst is prepared from the following ingredients by weight percent: 75-85wt% of graphene, 1.5-3.6wt% of platinum and 12.8-22.5wt% of nickel, and the sum of all percentages of all ingredients is 100%. The preparation method comprises the steps of preparing graphene oxide-tannic acid composite aqueous solution; adding nickel metallic ion solution to adjust the pH value to be 9-10, adding reducing agents and stirring for reaction, washing until the pH value of the supernatant liquid is 6.5-7, and taking precipitates at the lower layer to obtain the magnetic graphene-based platinum-nickel bimetallic catalyst. The magnetic graphene-based platinum-nickel bimetallic catalyst can be separated out of a reaction system thoroughly under an external magnetic field, and the recovery process is simple and efficient.
Description
Technical field
The present invention relates to a kind of catalyst.Particularly relate to a kind of magnetic graphite thiazolinyl platinum-nickel bimetal Catalysts and its preparation method.
Background technology
Metal/grapheme nanocomposite is very extensive in the application of catalytic field.Graphene not only has good electrical and thermal conductivity and heat endurance, and Stability Analysis of Structures.Wherein the Graphene of partial reduction or modified graphene surface have a certain amount of oxygen-containing functional group, and these groups can serve as the nuclearing centre of metal nanoparticle, impel it to grow.The standard two-dimensional structure of Graphene means the specific area of twice, active sites increase the increase that result in content of metal, decrease the reunion of metal nanoparticle simultaneously.Reactant can contact from upper and lower surface with catalytic active component, thus greatly improves reaction rate.In the metal catalytic category studied at present, wherein in the highest flight, the introducing of Graphene greatly reduces the consumption of noble metal to noble metal, and catalyst cost is effectively reduced, and this is significant to the large-scale production of catalyst and industrialization thereof.
At present, graphene-supported bimetallic correlative study report is relatively less.In a lot of situation, the second metal is introduced in certain simple metal nano particle, form the duplex metal nano granule of alloy, nucleocapsid or other special constructions, the catalytic activity stronger than monometallic, reaction selectivity and anti-poisoning capability can be shown, the cooperative reinforcing that the electron coordinate effect that the performance of these excellences is rooted in two kinds of metals brings.Graphene decorated with PtAu alloy nanoparticles:facile synthesis andpromising application for formic acid oxidation, Chem.Mat., 2011, the graphene-based plation type catalyst nano alloy composite catalyst that adopted two-step method to prepare in 23 (5): 1079-1081, obtained composite catalyst presents good catalytic activity in methanol oxidation.Three-dimensional Pt-on-Pd bimetallic nanodendrites supported ongraphene nanosheet:facile synthesis and used as an advanced nanoelectrocatalyst for methanoloxidation, Acs Nano, 2009, synthesize the dendritic Pt/Pd nano composite material of graphene-supported three-dimensional in 4 (1): 547-555, and be applied in methanol oxidation by the nanometer electrical catalyst as a kind of advanced person.
Although graphene-supported metal nano compound can as good heterogeneous catalysis, institute's carried metal mostly is as noble metals such as gold, silver, palladium, platinum, the recovery difficulty of these nanocatalysts in liquid-phase reaction system.Therefore, magnetic is utilized to provide the approach of a simple and fast to the recycling that graphene-based metallic catalyst is recovered as catalyst.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of magnetic graphite thiazolinyl platinum-nickel bimetal Catalysts and its preparation method utilizing magnetic to carry out recycling use.
The technical solution adopted in the present invention is: a kind of magnetic graphite thiazolinyl platinum-nickel bimetal catalyst, this catalyst take Graphene as carrier, at platinum-nickel alloy type duplex metal nano granule that Graphene supported on carriers particle diameter is 10 ~ 20nm, described platinum-nickel alloy type duplex metal nano granule is avtive spot, wherein nickel metal carrying is for magnetic, and the saturation magnetization of described catalyst at 15 DEG C ~ 35 DEG C is 8 ~ 13emu/g, with the percentages of described catalyst gross mass, Graphene 75 ~ 85wt%, platinum 1.5% ~ 3.6%wt%, nickel metal 12.8 ~ 22.5wt%, each constituent mass percentage sum is 100%.
A preparation method for magnetic graphite thiazolinyl platinum-nickel bimetal catalyst, comprises the steps:
1) in concentration be 0.8 ~ 1.2mg/mL graphene oxide water solution in add concentration in graphene oxide and the tannic acid mass ratio ratio that is 1:1 be that the tannic acid of 3 ~ 5mg/mL is as stabilizing agent, ultrasonic mixing, centrifugal to supernatant liquor without tannic acid, get lower sediment and obtain graphene oxide tannic acid mixture, in graphene oxide and distilled water mass ratio be the ratio of 1:8 ~ 12 by the graphene oxide tannic acid mixture ultrasonic disperse that obtains in distilled water, obtain graphene oxide tannic acid compound aqueous solution;
2) get step 1) prepared by graphene oxide tannic acid compound aqueous solution, be the ratio of 1:0.018 ~ 0.048:0.16 ~ 0.32 in the mass ratio of graphene oxide, platinum and nickel metal, the platinum solion that platinum ion concentration is 1 ~ 2mmol/L is added in graphene oxide tannic acid compound aqueous solution, add the nickel metal ion solution that nickel concentration of metal ions is 8 ~ 12mmol/L, regulate pH to 9 ~ 10 with NaOH, potassium hydroxide;
3) by with step 2) in the amount of molar ratio computing 1:2 ~ 3 of nickel metal that adds add the reducing agent that concentration is 0.1 ~ 0.3mmol/mL, stirring reaction 15 ~ 60min at 15 ~ 35 DEG C;
4) be 6.5 ~ 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer be deposited in-50 DEG C at freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Described platinum solion is chloroplatinic acid or the four potassium chloroplatinite aqueous solution.
Described nickel metal ion solution is nickel nitrate or nickel sulfate solution.
Described reducing agent is hydrazine hydrate, sodium borohydride and ascorbic acid wherein one or more.
Magnetic graphite thiazolinyl platinum-nickel bimetal Catalysts and its preparation method of the present invention, prepared magnetic graphite thiazolinyl platinum-nickel bimetal catalyst, when externally-applied magnetic field, can separate from reaction system comparatively up hill and dale, this removal process simple and effective.In addition, the present invention adopts simple one-step method to carry out catalyst preparing, and reaction condition is gentle, and with low cost, whole preparation process is all carried out in normal temperature, and without the need to high temperature, high pressure.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) figure of the magnetic graphite thiazolinyl platinum-nickel bimetal catalyst prepared by embodiment 1;
Fig. 2 is transmission electron microscope (TEM) figure of the magnetic graphite thiazolinyl platinum-nickel bimetal catalyst prepared by embodiment 1;
Fig. 3 is the magnetic graphite thiazolinyl platinum-nickel bimetal catalyst hysteresis curve at 300k prepared by embodiment 1;
Fig. 4 is that catalyst prepared by embodiment 1 is to the UV absorption spectrogram of catalytic reaction described in embodiment 5.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, magnetic graphite thiazolinyl platinum-nickel bimetal Catalysts and its preparation method of the present invention is described in detail.
Magnetic graphite thiazolinyl platinum-nickel bimetal catalyst of the present invention, take Graphene as carrier, at platinum-nickel alloy type duplex metal nano granule that Graphene supported on carriers particle diameter is 10 ~ 20nm, described platinum-nickel alloy type duplex metal nano granule is avtive spot, wherein nickel metal carrying is for magnetic, and the saturation magnetization of described catalyst at 15 DEG C ~ 35 DEG C is 8 ~ 13emu/g, with the percentages of described catalyst gross mass, Graphene 75 ~ 85wt%, platinum 1.5% ~ 3.6%wt%, nickel metal 12.8 ~ 22.5wt%, each constituent mass percentage sum is 100%.
The preparation method of magnetic graphite thiazolinyl platinum-nickel bimetal catalyst of the present invention, comprises the steps:
1) in concentration be 0.8 ~ 1.2mg/mL graphene oxide water solution in add concentration in graphene oxide and the tannic acid mass ratio ratio that is 1:1 be that the tannic acid of 3 ~ 5mg/mL is as stabilizing agent, ultrasonic mixing, centrifugal to supernatant liquor without tannic acid, get lower sediment and obtain graphene oxide tannic acid mixture, in graphene oxide and distilled water mass ratio be the ratio of 1:8 ~ 12 by the graphene oxide tannic acid mixture ultrasonic disperse that obtains in distilled water, obtain graphene oxide tannic acid compound aqueous solution;
2) get step 1) prepared by graphene oxide tannic acid compound aqueous solution, press with graphene oxide, the mass ratio of platinum and nickel metal is the ratio of 1:0.018 ~ 0.048:0.16 ~ 0.32, the platinum solion that platinum ion concentration is 1 ~ 2mmol/L is added in graphene oxide tannic acid compound aqueous solution, described platinum solion is chloroplatinic acid or the four potassium chloroplatinite aqueous solution, add the nickel metal ion solution that nickel concentration of metal ions is 8 ~ 12mmol/L, described nickel metal ion solution is nickel nitrate or nickel sulfate solution, with NaOH, potassium hydroxide regulates pH to 9 ~ 10,
3) by with step 2) in the amount of molar ratio computing 1:2 ~ 3 of nickel metal that adds add the reducing agent that concentration is 0.1 ~ 0.3mmol/mL, described reducing agent is hydrazine hydrate, sodium borohydride and ascorbic acid wherein one or more, stirring reaction 15 ~ 60min at 15 ~ 35 DEG C;
4) be 6.5 ~ 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer be deposited in-50 DEG C at freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Provide instantiation below:
First graphene oxide solution is made:
By 230mL mass fraction be 98% the concentrated sulfuric acid be cooled to 0 ~ 5 DEG C, add 10g graphite and 5g sodium nitrate, at 0 ~ 5 DEG C, stir 30min.Add 30g potassium permanganate, time reinforced, the temperature of reaction system must not more than 20 DEG C, to be fed complete, continue at reaction temperature being arranged on 35 DEG C to stir 30min, add 460mL water, be warming up to 98 DEG C and continue to stir 15min, add warm water, mixed solution is diluted to 1400mL, add 10mL mass fraction be 3% hydrogen peroxide remove unreacted potassium permanganate.By this mixed solution filtration under diminished pressure, wash with the watery hydrochloric acid of 500mL1M, then wash by 1000mL deionized water, centrifugal collecting precipitation under 10000r/min condition, is scattered in water, is prepared into graphene oxide water solution subsequently.
Embodiment 1:
Get the graphene oxide water solution that 100mL concentration is 0.8mg/mL, add the tannic acid aqueous solution that 20mL concentration is 4mg/mL, ultrasonic disperse 30 minutes, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 100mL distilled water.The chloroplatinic acid that 20mL concentration is 1mmol/L is added and 33mL concentration is the nickel sulfate solution of 12mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9, add the aqueous ascorbic acid that 2.64mL concentration is 0.3mmol/mL, stirring reaction 30min at 25 DEG C, be 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
The sign of the catalyst obtained by said method: as shown in Figure 1, transmission electron microscope as shown in Figure 2 for the SEM of product.Analysis shows that metallic particles is evenly distributed in graphene-based basal surface, and grain diameter is between 10 to 20nm.Product hysteresis curve at 300k as shown in Figure 3, measures magnetic field intensity scope from-10 to 10KOe.The saturated magnetization rate that can be obtained product by figure is 11.6emu/g, and does not almost have hysteresis or coercivity, shows that product obtained under normal temperature shows the character of superparamagnetic.
The application assessment of the catalyst obtained by said method: the reaction of reduction reaction as detecting catalyst activity adopting p-nitrophenol, course of reaction completes in quartz colorimetric utensil.Concrete steps are, add 2mL deionized water in silica dish, and adding 20 μ L concentration is wherein 10
-2the mol/L p-nitrophenol aqueous solution, then adds graphene-based platinum-nickel bimetal aqueous catalyst solution that 40 μ L concentration are 0.1mg/mL.At solution temperature is 25 DEG C, add 0.3mL concentration is wherein 0.1mol/L sodium borohydride aqueous solution, by ultraviolet specrophotometer, whole course of reaction is carried out to record and the analysis of absorption spectrum.Setting wavelength scanning range, at 200 ~ 600nm, is tested front deionized water and is eliminated background.Reaction test result as shown in Figure 4, the corresponding reactant p-nitrophenol of 400nm place absworption peak, 300nm place absworption peak correspondence product mutual-amino phenol.When not adding catalyst, the absorption peak strength at 400nm place did not even all change at several hours for several days, showed that p-nitrophenol is difficult to be reduced when not adding catalyst.After adding catalyst, 400nm place absworption peak constantly reduces, and strengthens, show that prepared graphene-based platinum-nickel bimetal catalyst has good catalytic activity along with 300nm place absworption peak.Above-mentioned after graphene-based platinum-nickel bimetal catalyst completes catalytic reaction in use, reaction vessel is placed in magnet other 5 minutes, can observe catalyst and be separated with solution and reunite on the sidewall being close to magnet side, reaction solution is clear state.Carefully pour out product, the catalyst of recovery directly can carry out catalytic reaction next time.
Embodiment 2:
Get the graphene oxide water solution that 50mL concentration is 1.2mg/mL, add the tannic acid aqueous solution that 20mL concentration is 3mg/mL, ultrasonic disperse 30min, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 50mL distilled water.The chloroplatinic acid that 4.5mL concentration is 2mmol/L is added and 28.3mL concentration is the nickel sulfate solution of 8mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9.5, add the aqueous ascorbic acid that 4.5mL concentration is 0.15mmol/mL, stirring reaction 15min at 15 DEG C, be 6.5 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Embodiment 3: get the graphene oxide water solution that 100mL concentration is 1mg/mL, add the tannic acid aqueous solution that 20mL concentration is 5mg/mL, ultrasonic disperse 30min, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 100mL distilled water.The chloroplatinic acid that 6.2mL concentration is 1.5mmol/L is added and 27.9mL concentration is the nickel sulfate solution of 10mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 10, add the aqueous ascorbic acid that 7mL concentration is 0.1mmol/mL, stirring reaction 60min at 35 DEG C, be 6.8 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Embodiment 4: get the graphene oxide water solution that 80mL concentration is 0.9mg/mL, add the tannic acid aqueous solution that 18mL concentration is 4mg/mL, ultrasonic disperse 30min, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 90mL distilled water.Four potassium chloroplatinites that 10.4mL concentration is 1.4mmol/L are added and 29.2mL concentration is the nickel sulfate solution of 11mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9.5, add the aqueous ascorbic acid that 4.8mL concentration is 0.18mmol/mL, stirring reaction 50min at 20 DEG C, be 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Embodiment 5: get the graphene oxide water solution that 60mL concentration is 1mg/mL, add the tannic acid aqueous solution that 15mL concentration is 4mg/mL, ultrasonic disperse 30min, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 72mL distilled water.The chloroplatinic acid that 4.5mL concentration is 2mmol/L is added and 28.3mL concentration is the nickel sulfate solution of 8mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9.5, add the sodium borohydride aqueous solution that 4.5mL concentration is 0.15mmol/mL, stirring reaction 15min at 15 DEG C, be 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Embodiment 6: get the graphene oxide water solution that 100mL concentration is 0.8mg/mL, add the tannic acid aqueous solution that 20mL concentration is 4mg/mL, ultrasonic disperse 30 minutes, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 100mL distilled water.Four potassium chloroplatinites that 20mL concentration is 1mmol/L are added and 33mL concentration is the nickel nitrate aqueous solution of 12mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9, add the hydrazine hydrate aqueous solution that 2.64mL concentration is 0.3mmol/mL, stirring reaction 30min at 25 DEG C, be 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Embodiment 7: get the graphene oxide water solution that 80mL concentration is 0.9mg/mL, add the tannic acid aqueous solution that 18mL concentration is 4mg/mL, ultrasonic disperse 30min, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 90mL distilled water.The chloroplatinic acid that 10.4mL concentration is 1.4mmol/L is added and 29.2mL concentration is the nickel nitrate aqueous solution of 11mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9.5, add the sodium borohydride aqueous solution that 4.8mL concentration is 0.18mmol/mL, stirring reaction 50min at 15 DEG C, be 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Embodiment 8: get the graphene oxide water solution that 80mL concentration is 0.9mg/mL, add the tannic acid aqueous solution that 18mL concentration is 4mg/mL, ultrasonic disperse 30min, graphene oxide is fully mixed with tannic acid, centrifuging and taking lower sediment obtains the graphene oxide after dewatering/tannic acid mixture, by its ultrasonic disperse in 90mL distilled water.Four potassium chloroplatinites that 10.4mL concentration is 1.4mmol/L are added and 29.2mL concentration is the nickel sulfate solution of 11mmol/L in prepared graphene oxide/tannic acid aqueous solution, drip the sodium hydrate aqueous solution of 1mol/L until pH is 9.5, add the hydrazine hydrate aqueous solution that 4.8mL concentration is 0.18mmol/mL, stirring reaction 45min at 22 DEG C, be 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer and be deposited in-50 DEG C of freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
Claims (5)
1. magnetic graphite thiazolinyl platinum-nickel bimetal catalyst, it is characterized in that, this catalyst take Graphene as carrier, at platinum-nickel alloy type duplex metal nano granule that Graphene supported on carriers particle diameter is 10 ~ 20nm, described platinum-nickel alloy type duplex metal nano granule is avtive spot, wherein nickel metal carrying is for magnetic, and the saturation magnetization of described catalyst at 15 DEG C ~ 35 DEG C is 8 ~ 13emu/g, with the percentages of described catalyst gross mass, Graphene 75 ~ 85wt%, platinum 1.5% ~ 3.6%wt%, nickel metal 12.8 ~ 22.5wt%, each constituent mass percentage sum is 100%.
2. a preparation method for magnetic graphite thiazolinyl platinum-nickel bimetal catalyst according to claim 1, is characterized in that, comprise the steps:
1) in concentration be 0.8 ~ 1.2mg/mL graphene oxide water solution in add concentration in graphene oxide and the tannic acid mass ratio ratio that is 1:1 be that the tannic acid of 3 ~ 5mg/mL is as stabilizing agent, ultrasonic mixing, centrifugal to supernatant liquor without tannic acid, get lower sediment and obtain graphene oxide tannic acid mixture, in graphene oxide and distilled water mass ratio be the ratio of 1:8 ~ 12 by the graphene oxide tannic acid mixture ultrasonic disperse that obtains in distilled water, obtain graphene oxide tannic acid compound aqueous solution;
2) get step 1) prepared by graphene oxide tannic acid compound aqueous solution, be the ratio of 1:0.018 ~ 0.048:0.16 ~ 0.32 in the mass ratio of graphene oxide, platinum and nickel metal, the platinum solion that platinum ion concentration is 1 ~ 2mmol/L is added in graphene oxide tannic acid compound aqueous solution, add the nickel metal ion solution that nickel concentration of metal ions is 8 ~ 12mmol/L, regulate pH to 9 ~ 10 with NaOH, potassium hydroxide;
3) by with step 2) in the amount of molar ratio computing 1:2 ~ 3 of nickel metal that adds add the reducing agent that concentration is 0.1 ~ 0.3mmol/mL, stirring reaction 15 ~ 60min at 15 ~ 35 DEG C;
4) be 6.5 ~ 7 with deionized water centrifuge washing to supernatant liquor pH, take off layer be deposited in-50 DEG C at freeze-drying, obtained magnetic graphite thiazolinyl platinum-nickel bimetal catalyst.
3. the preparation method of magnetic graphite thiazolinyl platinum-nickel bimetal catalyst according to claim 2, is characterized in that, described platinum solion is chloroplatinic acid or the four potassium chloroplatinite aqueous solution.
4. the preparation method of magnetic graphite thiazolinyl platinum-nickel bimetal catalyst according to claim 2, is characterized in that, described nickel metal ion solution is nickel nitrate or nickel sulfate solution.
5. the preparation method of magnetic graphite thiazolinyl platinum-nickel bimetal catalyst according to claim 2, is characterized in that, described reducing agent is hydrazine hydrate, sodium borohydride and ascorbic acid wherein one or more.
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| CN108641485A (en) * | 2018-04-13 | 2018-10-12 | 重庆市中光电显示技术有限公司 | Nickel-base composite conductive ink and preparation method thereof and the application in touch screen |
| CN109346110A (en) * | 2018-10-29 | 2019-02-15 | 东北师范大学 | Carbon-based nano laminated film and its manufacturing method applied to color hologram storage |
| CN112536042A (en) * | 2020-11-19 | 2021-03-23 | 福州大学 | Preparation method of methanol catalytic oxidation photoelectric catalyst |
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| CN112536042A (en) * | 2020-11-19 | 2021-03-23 | 福州大学 | Preparation method of methanol catalytic oxidation photoelectric catalyst |
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