CN111686759B - Preparation method of supported NiPd bimetallic catalyst and application of supported NiPd bimetallic catalyst in dehalogenation reaction - Google Patents

Preparation method of supported NiPd bimetallic catalyst and application of supported NiPd bimetallic catalyst in dehalogenation reaction Download PDF

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CN111686759B
CN111686759B CN202010595465.1A CN202010595465A CN111686759B CN 111686759 B CN111686759 B CN 111686759B CN 202010595465 A CN202010595465 A CN 202010595465A CN 111686759 B CN111686759 B CN 111686759B
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nipd
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bimetallic catalyst
deionized water
graphene oxide
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CN111686759A (en
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黄飞
王溪溪
汪婧
孙金余
李长江
兰艳素
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Huangshan University
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Abstract

The invention belongs to the technical field of bimetallic catalyst preparation, and particularly relates to a preparation method of a supported NiPd bimetallic catalyst and application of the supported NiPd bimetallic catalyst in dehalogenation. The supported NiPd bimetallic catalyst provided by the invention is mainly prepared from sodium chloropalladate, nickel chloride, graphene oxide and sodium borohydride serving as raw materials. The NiPd bimetallic catalyst has the advantages of more adjustability and controllability, high catalytic activity, stronger magnetism, capability of being separated by centrifugation or magnetic force and high cyclic utilization rate; the NiPd bimetallic catalyst is particularly suitable for dehalogenation reaction, has high catalytic activity and catalytic efficiency and excellent stability, and after 10 times of cyclic use, the conversion rate is 99 percent, and the selectivity is still more than 99 percent.

Description

Preparation method of supported NiPd bimetallic catalyst and application of supported NiPd bimetallic catalyst in dehalogenation reaction
Technical Field
The invention belongs to the technical field of bimetallic catalyst preparation, and particularly relates to a preparation method of a supported NiPd bimetallic catalyst, and further relates to application of the catalyst in dehalogenation.
Background
Regarding the synthesis of Ni-Pd catalyst, CN2219170Y discloses a device for preparing a nano NiPd catalyst, which is composed of a vacuum chamber, a cold trap, a cathode, an anode and the like, and is used for preparing two high-melting-point metals, namely nickel and palladium with similar melting points, into an alloy.
Regarding the effect of the synthesis process of Ni-Pd catalyst on the catalytic performance, adriano H.Braga et al decomposed the metal-organic precursor Ni (cod) 2 And Pd 2 (dba) 3 Bimetallic Ni-Pd and Ni and Pd reference catalysts are prepared, so that nano particles with the particle size of 3-6 nm are obtained, and the following two different synthetic methods are disclosed: firstly, fixation: i.e. solution synthesis with encapsulated ligand (hexadecylamine) and then impregnation of the preformed nanoparticles in SiO 2 On a carrier; the other is a direct decomposition method: i.e. the precursor is directly decomposed to SiO 2 No stabilizer is added on the carrier.
The above article mainly focuses on the research on the influence of the synthesis process of the Ni-Pd catalyst on the catalytic performance, and especially researches on the influence of the Ni-Pd alloy catalyst rich in nickel, the Ni-Pd alloy catalyst rich in palladium, and the pure Pd and pure Ni catalysts prepared by the above two different synthesis methods on the catalytic selectivity, but no relevant disclosure is made on the application or application effect of the NiPd bimetallic catalyst.
Therefore, it is necessary to invent a preparation method of a supported NiPd bimetallic catalyst with excellent catalytic activity, stability and recycling performance, and further research is carried out on the application thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a supported NiPd bimetallic catalyst with excellent catalytic activity, stability and recycling performance;
the invention also provides the application and the application effect of the supported NiPd bimetallic catalyst in dehalogenation reaction;
the preparation method of the supported NiPd bimetallic catalyst provided by the invention comprises the following steps:
(1) Adding sodium chloropalladate and nickel chloride into the first part of deionized water until the sodium chloropalladate and the nickel chloride are completely dissolved in the deionized water;
(2) Adding graphene oxide into the second part of deionized water, so that the graphene oxide is completely dissolved in the second part of deionized water to obtain a graphene oxide aqueous solution;
(3) Dropwise adding the graphene oxide aqueous solution into the material dissolved in the step (1) and uniformly mixing;
(4) Dissolving sodium borohydride in the third part of deionized water to obtain a sodium borohydride solution;
(5) Heating and stirring the materials in the step (3), dropwise adding the sodium borohydride solution in the step (4) for reaction, cooling, and standing to obtain a reaction solution;
(6) And (5) centrifuging and washing the reaction liquid to obtain the supported NiPd bimetallic catalyst.
Preferably, in the step (1), the mass ratio of the sodium chloropalladate to the nickel chloride is as follows: (0.08-0.12): (0.02-0.03);
preferably, in the step (1), the mass-to-volume ratio of the sodium chloropalladate, the nickel chloride and the first part of deionized water is as follows: (0.08-0.12) g: (0.025 to 0.028) g: (18-22) mL;
preferably, in the step (1), the mass-to-volume ratio of the sodium chloropalladate, the nickel chloride and the deionized water is as follows: 0.1g:0.0269g:20mL;
preferably, in (1), the sodium chloropalladate and the nickel chloride are completely dissolved in the deionized water by magnetic stirring.
(2) In the method, the mass volume ratio of the graphene oxide to the second part of deionized water is (4-6) mg: (0.9-1.1) mL;
preferably, (2), performing ultrasonic treatment until the graphene oxide is completely dissolved in the second part of deionized water;
preferably, in the step (2), ultrasonic treatment is carried out for 1.5-2.5 hours until the graphene oxide is completely dissolved in the second part of deionized water;
preferably, (2), the ultrasonic treatment is carried out for 2 hours until the graphene oxide is completely dissolved in the second part of deionized water.
Preferably, (3) dropwise adding the graphene oxide aqueous solution into the materials dissolved in the step (1) to uniformly mix the materials; the dropping speed is 58-62 drops/min, ultrasonic treatment is carried out while dropping, and ultrasonic treatment is continued for 0.8-1.2 hours after dropping is finished, so that the graphene oxide aqueous solution, the sodium chloropalladate and the nickel chloride solution are uniformly mixed;
preferably, (3) dropwise adding the graphene oxide aqueous solution into the material in the step (1) to uniformly mix the materials; the dropping speed is 60 drops/min, ultrasonic treatment is carried out while dropping, and ultrasonic treatment is continued for 1h after dropping is finished, so that the graphene oxide aqueous solution is uniformly mixed with the sodium chloropalladate and the nickel chloride solution;
(3) In the method, the mass ratio of the sodium chloropalladate to the graphene oxide is (0.09-0.12) g:50mg;
preferably, in the step (3), the mass ratio of sodium chloropalladate to graphene oxide is 0.1g:50mg.
(4) In the method, the mass volume ratio of the sodium borohydride to the third part of deionized water is as follows: (0.8-1.1) g: (23-27) mL;
preferably, in the step (4), the mass-to-volume ratio of the sodium borohydride to the third part of deionized water is: 0.993g:25mL.
(5) Heating the material obtained in (3) in an oil bath and simultaneously magnetically stirring; the magnetic stirring speed is 1100-1300 r/min; when the oil bath is heated, the temperature is gradually increased to 82-86 ℃ at the speed of 2-6 ℃/min, the sodium borohydride solution in the step (4) is added dropwise within 20-40 min, then the reaction is continuously carried out for 2-4 h under the condition of keeping the temperature at 82-86 ℃ in the oil bath by magnetic stirring, after the reaction is finished, the reaction solution is cooled to the room temperature, and the obtained reaction solution is kept still for 10-14 h;
the volume-mass ratio of the sodium borohydride solution to the sodium chloropalladate is (0.9-1.1) mL: (0.08-0.12) g;
preferably, in the step (5), the material in the step (3) is subjected to oil bath heating and magnetic stirring, wherein the magnetic stirring speed is 1200r/min; heating in oil bath, gradually heating to 84 ℃ at the speed of 4 ℃/min, completing dropwise adding of the sodium borohydride solution in the step (4) within 30min, keeping the solution in the oil bath at 84 ℃, magnetically stirring for continuous reaction for 3h, cooling to room temperature after the reaction is finished, and standing the obtained reaction solution for 12h;
the volume-to-mass ratio of the sodium borohydride solution to the sodium chloropalladate is 1mL:0.1g.
(6) Centrifuging the reaction solution in the step (5) at the rotating speed of 13000-15000 r/min for 15-25 min, washing with water, and then washing with alcohol to obtain a supported NiPd bimetallic catalyst;
preferably, (6) centrifuging the reaction solution in the step (5) for 15-25 min at the rotating speed of 13000-15000 r/min, keeping the precipitate, washing the precipitate for 3 times by using deionized water, and then washing the precipitate for 3 times by using absolute ethyl alcohol; centrifuging after each washing, wherein the rotating speed of each centrifuging is 13000-15000 r/min, and the time is 15-25 min; washing to obtain a supported NiPd bimetallic catalyst;
preferably, (6) centrifuging the reaction solution in the step (5) for 20min at the rotating speed of 14000r/min, keeping the precipitate, washing the precipitate for 3 times by using deionized water, and then washing the precipitate for 3 times by using absolute ethyl alcohol; centrifuging after each washing, wherein the rotating speed of each centrifuging is 14000r/min, and the time is 20min; and washing to obtain the supported NiPd bimetallic catalyst.
The steps also comprise (7), the supported NiPd bimetallic catalyst obtained in the step (6) is dried in vacuum and milled to obtain a powdery supported NiPd bimetallic catalyst;
preferably, the method also comprises (7), the supported NiPd bimetallic catalyst obtained in the step (6) is placed in a vacuum drying oven to be dried for 22-26 h under the temperature of 50-70 ℃ in vacuum, and the catalyst is ground to obtain the powdered supported NiPd bimetallic catalyst;
preferably, the method also comprises (7), the supported NiPd bimetallic catalyst obtained in the step (6) is placed in a vacuum drying oven to be dried for 24 hours in vacuum at 60 ℃, and the catalyst is ground to obtain the powdered supported NiPd bimetallic catalyst.
The preparation method of the supported NiPd bimetallic catalyst comprises the following steps:
(1) Adding sodium chloropalladate and nickel chloride into the first part of deionized water, and magnetically stirring until the sodium chloropalladate and the nickel chloride are completely dissolved in the deionized water;
the mass-volume ratio of the sodium chloropalladate to the nickel chloride to the first part of deionized water is as follows: (0.08-0.12) g: (0.025 to 0.028) g: (18-22) mL;
the mass ratio of the sodium chloropalladate to the nickel chloride is as follows: (0.08-0.12): (0.02-0.03);
(2) Adding graphene oxide into a second part of deionized water, and performing ultrasonic treatment to completely dissolve the graphene oxide into the second part of deionized water to obtain a graphene oxide aqueous solution;
the mass volume ratio of the graphene oxide to the second part of deionized water is (4-6) mg: (0.9-1.1) mL;
(3) Dropwise adding the graphene oxide aqueous solution into the materials dissolved in the step (1) to uniformly mix the materials; the dropping speed is 58-62 drops/min, ultrasonic treatment is carried out while dropping, and ultrasonic treatment is continued for 0.8-1.2 hours after dropping is finished, so that the graphene oxide aqueous solution, the sodium chloropalladate and the nickel chloride solution are uniformly mixed;
before mixing, the mass ratio of the sodium chloropalladate to the graphene oxide is (0.09-0.12) g:50mg;
(4) Dissolving sodium borohydride in the third part of deionized water to obtain a sodium borohydride solution; the mass volume ratio of the sodium borohydride to the third part of deionized water is as follows: (0.8-1.1) g: (23-27) mL;
(5) Heating the material obtained in the step (3) in an oil bath and simultaneously carrying out magnetic stirring; the magnetic stirring speed is 1100-1300 r/min; when the oil bath is heated, gradually heating to 82-86 ℃ at the speed of 2-6 ℃/min, completing dropwise adding of the sodium borohydride solution in the step (4) within 20-40 min, continuing to magnetically stir for continuous reaction for 2-4 h while keeping the temperature at 82-86 ℃ in the oil bath, cooling to room temperature after the reaction is finished, and standing the obtained reaction liquid for 10-14 h;
the volume-mass ratio of the sodium borohydride solution to the sodium chloropalladate is (0.9-1.1) mL: (0.08-0.12) g;
(6) And (4) centrifuging the reaction solution in the step (5) at the rotating speed of 13000-15000 r/min for 15-25 min, washing with water, and then washing with alcohol to obtain the supported NiPd bimetallic catalyst.
The application of the supported NiPd bimetallic catalyst in dehalogenation reaction is also within the protection scope of the invention.
The invention has the beneficial effects that:
(1) Compared with single metal nanoparticles, the catalyst provided by the invention has more controllability, the particle size and the morphology of the nanoparticles can be controlled by controlling the relative proportion of two metals, and a synergistic effect is generated between two metal atoms;
(2) Electrons can be transferred between two metal atoms, and can also form competitive transfer between the two atoms and a reduced graphene oxide interface, so that the electronic state of active atoms can be controlled, and the catalytic activity of the catalyst is improved;
(3) The transition metal ions are introduced, so that the nano-catalyst can be induced to generate different exposed surfaces, and the catalytic activity of the nano-catalyst can be regulated and controlled;
(4) Transition metal is doped in the single noble metal nano-particle, so that the using amount of the noble metal can be effectively reduced, and the cost of the catalyst is further reduced;
(5) The catalyst has stronger magnetism, can be separated by centrifugation or magnetic force, and has high recycling rate.
Drawings
FIG. 1 shows Ni 1 Pd 3 @ rGO transmission electron microscopy images;
FIG. 2Ni 1 Pd 3 @ rGO high resolution transmission electron microscopy images;
FIG. 3 shows Ni 1 Pd 3 @rGO、Ni 1 Pd 1 @ rGO and Ni 3 Pd 1 @ rGO X-ray powder diffraction pattern;
FIG. 4 shows Ni 1 Pd 3 A bar graph of @ rGO catalytic cycle conversion and selectivity;
fig. 5 is a structural diagram of graphene oxide and a supported metal.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
Example 1
The preparation method of the supported NiPd bimetallic catalyst comprises the following steps:
(1) Accurately weighing 0.1g of sodium chloropalladate (Na) 2 PdCl 4 ) 0.0269g of nickel chloride (NiCl) 2 ·6H 2 O) and 20mL of deionized water are added into a 100mL round-bottom flask A, and the solution is completely dissolved in the deionized water by magnetic stirring, so that the solution is transparent and reddish brown;
(2) Adding pre-prepared 50mg of Graphene Oxide (GO) and 10mL of deionized water into a 100mL round-bottom flask B, and carrying out ultrasonic treatment for 2 hours until the graphene oxide is completely dissolved in the deionized water, wherein the solution is mud yellow;
(3) Dropwise adding the graphene oxide aqueous solution in the round-bottom flask B into the round-bottom flask A at a dropping speed of about 60 drops per minute, carrying out ultrasonic treatment while dropwise adding, and continuing to carry out ultrasonic treatment for 1h after dropwise adding is finished so as to uniformly mix the graphene oxide aqueous solution with sodium chloropalladate and nickel chloride solution;
(4) Accurately weigh 0.9930g of sodium borohydride (NaBH) 4 ) Dissolving in 25mL of deionized water, preparing a sodium borohydride solution with the quantity concentration of 1.05mol/L, and standing for later use;
(5) Placing the round bottom flask A in an oil bath pan for magnetic stirring, wherein the magnetic stirring speed is 1200r/min, gradually raising the oil bath temperature to 84 ℃, and the temperature raising speed is 4 ℃/min; 1mL of 1.05mol/L sodium borohydride solution is sucked by a 1mL syringe and suspended in the mouth of the round bottom flask A, 1mL of the sodium borohydride solution is freely and dropwise added into the round bottom flask A within 30min, the solution is gradually turned into black from reddish brown, and the oil bath is heated and the magnetic stirring is carried out for 3 hours continuously; after the reaction is finished, cooling to room temperature, and standing for 12 hours;
(6) Placing the reaction solution in a centrifuge tube, centrifuging for 20min at 14000r/min, slowly sucking the supernatant solution in the centrifuge tube with a rubber-tipped dropper after centrifuging, and keeping the bottom of the centrifuge tubePartially precipitating, washing the precipitate with deionized water for 3 times, washing with anhydrous ethanol for 3 times to completely remove other impurities in the precipitate, centrifuging after each washing to remove the upper layer solution, wherein the centrifuging time is 20min and the rotating speed is 14000r/min; obtaining the load type bimetal Ni 1 Pd 3 @ rGO catalyst (as shown in figure 1);
(7) And (3) putting the catalyst obtained in the step (6) into a vacuum drying oven, drying the catalyst in vacuum for 24h at the temperature of 60 ℃, and fully grinding the catalyst into fine black powder by using a quartz grinding bowl for three times to obtain the powdery supported NiPd bimetallic catalyst.
Example 2
The inventors performed Transmission Electron Microscopy (TEM), high Resolution Transmission Electron Microscopy (HRTEM), and X-ray powder diffraction (XRD) characterization on the supported NiPd bimetallic catalyst obtained in example 1, with the following results:
1. transmission Electron Microscopy (TEM) characterization
Transmission Electron Microscope (TEM) is used for Ni 1 Pd 3 The @ rGO catalyst is characterized by being uniformly dispersed and uniform in size, having no obvious agglomeration phenomenon and having a particle size of about 4nm as shown in FIGS. 1 (a) and (b).
2. High Resolution Transmission Electron Microscopy (HRTEM) characterization
High Resolution Transmission Electron Microscopy (HRTEM) on Ni 1 Pd 3 The @ rGO catalyst was characterized as having a lattice spacing of 0.210nm, as shown in FIG. 2.
Characterization by X-ray powder diffraction (XRD)
To Ni 1 Pd 3 @rGO、Ni 1 Pd 1 @rGO、Ni 3 Pd 1 X-ray powder diffraction (XRD) characterization of @ rGO, as shown in FIG. 3, ni can be seen 1 Pd 1 Characteristic peak of @ rGO is at Ni 1 Pd 3 @ rGO and Ni 3 Pd 1 The middle of @ rGO, indicates that the content of Ni and Pd has an effect on its XRD peak position.
Example 3
The supported NiPd bimetallic catalyst obtained in the example 1 is applied to the dehalogenation reaction of the halogenated aromatic hydrocarbon, and the specific steps are as follows:
1.Ni 1 Pd 3 optimization of reaction conditions for catalyzing chlorobenzene dechlorination by @ rGO
In the field of catalytic chemistry, noble metals which are expensive and not readily available, such as gold (Au), ruthenium (Ru), rhodium (Rh), iridium (Ir), platinum (Pt), and the like, are mainly used as catalysts. In the invention, the reduced graphene oxide (Ni) is loaded with metal Ni and transition metal Pd which are low in price and extremely easy to obtain 1 Pd 3 @ rGO) as a catalyst, has very important significance in catalytic chemistry, and therefore Ni 1 Pd 3 The @ rGO shows wide application prospect in the catalytic industry.
Ni 1 Pd 3 The application of @ rGO in the catalytic chlorobenzene dechlorination reaction comprises the following steps:
accurately weigh 10mgNi 1 Pd 3 Adding the @ rGO catalyst into a 100mL reaction tube, adding 3mL deionized water as a solvent, and putting the mixture into an ultrasonic instrument for ultrasonic treatment for 20min to enable Ni to be in contact with the solvent 1 Pd 3 @ rGO is fully dispersed in deionized water, and 1mmol of chlorobenzene and 1mmol of sodium borohydride (NaBH) are added 4 ) Magnetically stirring at 25 deg.C for 2 hr at 1200 rpm, extracting with ethyl acetate as extractant to obtain reaction product, and performing qualitative and quantitative test by gas chromatography and gas chromatography-mass spectrometry (GC-MS), wherein Ni is 1 Pd 3 The conversion rate and selectivity of the @ rGO catalyst in catalyzing chlorobenzene dechlorination to benzene are both more than 99%.
The inventor carries out screening optimization on experimental factors such as catalyst type, catalyst dosage, hydrogen source type, hydrogen source dosage, solvent type, reaction temperature, reaction time and the like, and the optimal conditions are as follows:
10mgNi 1 Pd 3 the reaction method comprises the following steps of taking @ rGO as a catalyst, 3mL of deionized water as a solvent, sodium borohydride as a hydrogen source, wherein the dosage of the sodium borohydride is 1mmol, the reaction temperature is 25 ℃, the reaction time is 2 hours, the conversion rate and the selectivity of the catalytic chlorobenzene dechlorination reaction are both more than 99%, and the experimental results are shown in Table 1.
TABLE 1 Ni 1 Pd 3 Optimization of reaction conditions for catalyzing chlorobenzene dechlorination by @ rGO
Figure BDA0002555804540000091
* The reaction was carried out under air atmosphere with 1mmol of chlorobenzene and 3mL of a solvent.
a The yield of the target product is determined by GC.
2.Ni 1 Pd 3 @ rGO catalytic dehalogenation reaction of halogenated aromatic hydrocarbon
Under the optimum condition (10 mgNi) 1 Pd 3 The method is characterized in that @ rGO is used as a catalyst, 3mL of deionized water is used as a solvent, the amount of sodium borohydride is 1mmol (the amount of sodium borohydride of polyhalogenated aromatic hydrocarbon is 1mmol multiple of the number of halogen-containing atoms), the reaction temperature is 25 ℃ or 50 ℃, the reaction time is 2h or 5 h), the inventor researches the dehalogenation reaction of the halogenated aromatic hydrocarbon, the conversion rate is more than 97%, the selectivity is more than 99%, and the experimental results are shown in Table 2.
TABLE 2 dehalogenation of halogenated aromatic hydrocarbons
Figure BDA0002555804540000101
Figure BDA0002555804540000111
Figure BDA0002555804540000121
Reaction conditions are 1mmol of polyhalogenated aromatic hydrocarbon and 1mmol of NaBH 4 ，10mg Ni 1 Pd 3 @rGO，3mL H 2 O, stirring for 2h at 25 ℃ in an air atmosphere.
a The yield of the target product is determined by GC.
b 1mmol of polyhalogenated aromatic hydrocarbon, naBH 4 (the dosage of sodium borohydride is 1mmol times of the number of halogen-containing atoms), 10mg of Ni 1 Pd 3 @rGO，3mL H 2 O, stirring for 5h at 50 ℃ in an air atmosphere.
Example 4
With respect to Ni obtained in example 1 1 Pd 3 The inventor of the invention researches the usability of the @ rGO catalytic chlorobenzene dechlorination reaction, and the result is as follows:
after 10 times of recycling, the conversion rate of the catalyst in the example 1 is 99%, and the selectivity is still more than 99%, as shown in figure 4, which shows that the catalyst has better catalytic activity, stability and recycling performance.
Thus, from the above experiments it can be seen that:
(1) The catalyst of the invention has the following advantages:
the catalyst has more controllability, high catalytic activity and stronger magnetism, and can be separated by centrifugation or magnetic force, so that the cyclic utilization rate is high;
(2) The load graphene oxide has the advantages that:
graphene Oxide (GO) has a large surface area, has many hydroxyl (-OH), carbonyl (-C = O), carboxyl (-COOH), and other groups on its surface, can be used as a good dispersion carrier, has obvious supporting and anchoring effects on the alloy nanoparticles, helps to control the size and distribution of metal particles formed during synthesis, and achieves a good monodispersion purpose, as shown in fig. 5. Therefore, the metal is loaded on the graphene oxide, so that the dispersity of the nano particles can be better improved, the agglomeration of the nano particles in the catalytic process is reduced, the catalytic activity and the catalytic efficiency of the nano particles are improved, and the recycling rate of the catalyst in the reaction can be improved.
(3)Ni 1 Pd 3 The advantages of the reaction of catalyzing chlorobenzene dechlorination by @ rGO:
Ni 1 Pd 3 the catalyst has the conversion rate of 99% and the selectivity of more than 99% after 10 times of recycling, which indicates that the catalyst has better catalytic activity and stability.

Claims (4)

1. The application of the supported NiPd bimetallic catalyst in dehalogenation reaction is characterized in that the preparation method of the supported NiPd bimetallic catalyst comprises the following steps:
(1) Adding sodium chloropalladate and nickel chloride into the first part of deionized water until the sodium chloropalladate and the nickel chloride are completely dissolved in the deionized water;
(2) Adding graphene oxide into a second part of deionized water, and performing ultrasonic treatment until the graphene oxide is completely dissolved in the second part of deionized water to obtain a graphene oxide aqueous solution;
(3) Dropwise adding the graphene oxide aqueous solution into the material in the step (1) to uniformly mix the materials; the dropping speed is 60 drops/min, ultrasonic treatment is carried out while dropping, and ultrasonic treatment is continued for 1h after dropping is finished, so that the graphene oxide aqueous solution, the sodium chloropalladate and the nickel chloride solution are uniformly mixed; the mass ratio of the sodium chloropalladate to the graphene oxide is (0.09-0.12) g:50mg;
(4) Dissolving sodium borohydride in the third part of deionized water to obtain a sodium borohydride solution;
(5) Heating the material obtained in the step (3) in an oil bath and simultaneously carrying out magnetic stirring; the magnetic stirring speed is 1100-1300 r/min; when the oil bath is heated, gradually heating to 82-86 ℃ at the speed of 2-6 ℃/min, completing dropwise adding of the sodium borohydride solution in the step (4) within 20-40 min, continuing to magnetically stir for continuous reaction for 2-4 h while keeping the temperature at 82-86 ℃ in the oil bath, cooling to room temperature after the reaction is finished, and standing the obtained reaction liquid for 10-14 h;
(6) Centrifuging and washing the reaction liquid in the step (5) to obtain a supported NiPd bimetallic catalyst;
wherein, in 1), the mass-to-volume ratio of the sodium chloropalladate, the nickel chloride and the first part of deionized water is as follows: (0.08-0.12) g: (0.025 to 0.028) g: (18-22) mL;
(4) In the method, the mass volume ratio of the sodium borohydride to the third part of deionized water is as follows: (0.8-1.1) g: (23-27) mL;
the volume-mass ratio of the sodium borohydride solution to the sodium chloropalladate is (0.9-1.1) mL: (0.08-0.12) g.
2. The use of claim 1, wherein in (2), the mass-to-volume ratio of graphene oxide to the second portion of deionized water is (4-6) mg: (0.9-1.1) mL.
3. The use of claim 1, wherein in (6), the reaction solution in (5) is centrifuged at 13000-15000 r/min for 15-25 min, washed with water and then alcohol to obtain the supported NiPd bimetallic catalyst.
4. The use according to claim 1, further comprising (7) drying the supported NiPd bimetallic catalyst obtained in (6) under vacuum and milling to obtain a powdered supported NiPd bimetallic catalyst.
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