CN111686759A - 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 PDFInfo
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- CN111686759A CN111686759A CN202010595465.1A CN202010595465A CN111686759A CN 111686759 A CN111686759 A CN 111686759A CN 202010595465 A CN202010595465 A CN 202010595465A CN 111686759 A CN111686759 A CN 111686759A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 12
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 53
- 239000011734 sodium Substances 0.000 claims abstract description 42
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 41
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
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- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 40
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- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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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
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 an application of the catalyst in dehalogenation.
Background
Regarding the synthesis of Ni-Pd catalyst, CN2219170Y discloses a device for preparing nano NiPd catalyst, which is composed of vacuum chamber, cold trap, cathode, anode, etc. and is used to prepare two kinds of high melting point metals with similar melting points into alloy, and the above-mentioned documents do not disclose the preparation method.
Regarding the effect of the synthesis process of Ni-Pd catalysts on catalytic performance, Adriano H.Braga et al, by decomposition of the metal-organic precursor Ni (cod)2And Pd2(dba)3Preparing bimetallic Ni-Pd and Ni-Pd reference catalyst to obtain nano particles with the particle size of 3-6 nm,and discloses two different synthetic methods as follows: firstly, fixation: i.e. solution synthesis with encapsulated ligand (hexadecylamine) and then impregnation of the preformed nanoparticles in SiO2On a carrier; the other is a direct decomposition method: i.e. the precursor is directly decomposed to SiO2On the carrier, no stabilizer is added.
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 a 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: (0.025-0.028) 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: 0.1 g: 0.0269 g: 20 mL;
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 graphene oxide is fully dissolved in the second deionized water after ultrasonic treatment for 2 h.
Preferably, (3) dropwise adding the graphene oxide aqueous solution into the materials dissolved in the step (1) to uniformly mix the materials; the dropping rate 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 is uniformly mixed with the sodium chloropalladate and the nickel chloride solution;
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: 50 mg;
preferably, in the step (3), the mass ratio of sodium chloropalladate to graphene oxide is 0.1 g: 50 mg.
(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: 0.993 g: 25 mL.
(5) Heating the material obtained in (3) in an oil bath and simultaneously magnetically stirring; the magnetic stirring speed is 1100-1300 r/min; gradually heating to 82-86 ℃ at the speed of 2-6 ℃/min during oil bath heating, dropwise adding the sodium borohydride solution in the step (4) within 20-40 min, continuously magnetically stirring for continuously reacting 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-to-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 1200 r/min; heating in an oil bath, gradually heating to 84 ℃ at the speed of 4 ℃/min, dropwise adding the sodium borohydride solution in the step (4) within 30min, keeping the solution in the oil bath at 84 ℃, magnetically stirring for continuously reacting for 3h, cooling to room temperature after the reaction is finished, and standing the obtained reaction solution for 12 h;
the volume-to-mass ratio of the sodium borohydride solution to the sodium chloropalladate is 1 mL: 0.1 g.
(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) at the rotating speed of 13000-15000 r/min for 15-25 min, keeping the precipitate, washing the precipitate with deionized water for 3 times, and then washing the precipitate with absolute ethyl alcohol for 3 times; 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 20 min; 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 ℃, and the dried NiPd bimetallic catalyst is ground 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 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: (0.025-0.028) 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 rate 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 is uniformly mixed with the sodium chloropalladate and the nickel chloride solution;
before mixing, the mass ratio of sodium chloropalladate to graphene oxide is (0.09-0.12) g: 50 mg;
(4) dissolving sodium borohydride in a 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; gradually heating to 82-86 ℃ at the speed of 2-6 ℃/min during oil bath heating, dropwise adding the sodium borohydride solution in the step (4) within 20-40 min, continuously magnetically stirring for continuously reacting 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-to-mass ratio of the sodium borohydride solution to the sodium chloropalladate is (0.9-1.1) mL: (0.08-0.12) g;
(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 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 Ni1Pd3@ rGO transmission electron microscopy images;
FIG. 2Ni1Pd3@ rGO high resolution transmission electron microscopy images;
FIG. 3 shows Ni1Pd3@rGO、Ni1Pd1@ rGO and Ni3Pd1@ rGO X-ray powder diffraction pattern;
FIG. 4 shows Ni1Pd3A 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)2PdCl4) 0.0269g of nickel chloride (NiCl)2·6H2O) 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 at the bottle 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 changed into black from reddish brown, and the oil bath is heated and magnetically stirred for 3 hours; after the reaction is finished, cooling to room temperature, and standing for 12 hours;
(6) placing the reaction solution in a centrifuge tube for centrifuging for 20min, wherein the rotating speed of the centrifuge is 14000r/min, after centrifuging, slowly absorbing the upper layer solution in the centrifuge tube by using a rubber-tipped dropper to remove, reserving the sediment at the bottom of the centrifuge tube, washing the sediment for 3 times by using deionized water, washing for 3 times by using absolute ethyl alcohol, completely removing other impurities in the sediment, centrifuging after each washing, and removing the upper layer solution, wherein the centrifuging time is 20min and the rotating speed is 14000 r/min; obtaining the load type bimetal Ni1Pd3@ 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 Ni1Pd3The @ 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 Ni1Pd3The @ 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 Ni1Pd3@rGO、Ni1Pd1@rGO、Ni3Pd1X-ray powder diffraction (XRD) characterization of @ rGO, as shown in FIG. 3, Ni can be seen1Pd1Characteristic peak of @ rGO is at Ni1Pd3@ rGO and Ni3Pd1The 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.Ni1Pd3optimization 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 obtain1Pd3@ rGO) as a catalyst, has very important significance in catalytic chemistry, and therefore Ni1Pd3@ rGO shows wide application prospects in the catalytic industry.
Ni1Pd3The application of @ rGO in the catalytic chlorobenzene dechlorination reaction comprises the following steps:
accurately weigh 10mgNi1Pd3Adding 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 solvent1Pd3@ rGO is fully dispersed in deionized water, and then 1mmol of chlorobenzene and 1mmol of sodium borohydride (NaBH) are added4) Magnetically stirring at 25 deg.C for 2 hr at 1200 rpm, and extracting with ethyl acetate as extractantTaking out the reaction product, performing qualitative and quantitative test by gas chromatography and gas chromatography-mass spectrometry (GC-MS), and measuring Ni1Pd3The 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:
10mgNi1Pd3the 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 Ni1Pd3Optimization of reaction conditions for catalyzing chlorobenzene dechlorination by @ rGO
Reaction conditions 1mmol of chlorobenzene, 3mL of solvent, stirring under air atmosphere.
aThe yield of the target product is determined by GC.
2.Ni1Pd3@ rGO catalytic dehalogenation reaction of halogenated aromatic hydrocarbon
Under the optimum condition (10 mgNi)1Pd3The 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 5h), 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
Reaction conditions are 1mmol of polyhalogenated aromatic hydrocarbon and 1mmol of NaBH4，10mg Ni1Pd3@rGO，3mL H2O, stirring for 2h at 25 ℃ in an air atmosphere.
aThe yield of the target product is determined by GC.
b1mmol of polyhalogenated aromatic hydrocarbon, NaBH4(the dosage of the sodium borohydride is 1mmol times of the number of the halogen atoms), 10mgNi1Pd3@rGO，3mL H2O, stirring for 5h at 50 ℃ in an air atmosphere.
Example 4
With respect to Ni obtained in example 11Pd3The 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 the 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 in the synthesis process, 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)Ni1Pd3The advantages of the reaction of catalyzing chlorobenzene dechlorination by @ rGO:
Ni1Pd3the 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 (10)
1. 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 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 a 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.
2. The method for preparing the supported NiPd bimetallic catalyst as described in claim 1, wherein in (1), the mass ratio of sodium chloropalladate to nickel chloride in (1) is as follows: (0.08-0.12): (0.02-0.03);
preferably, the mass-to-volume ratio of the sodium chloropalladate, the nickel chloride and the first portion of deionized water is as follows: (0.08-0.12) g: (0.025-0.028) 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: 0.1 g: 0.0269 g: 20 mL;
preferably, in (1), the sodium chloropalladate and the nickel chloride are completely dissolved in the deionized water by magnetic stirring.
3. The preparation method of the supported NiPd bimetallic catalyst as described in claim 1, wherein in the step (2), the mass-to-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 graphene oxide is fully dissolved in the second deionized water after ultrasonic treatment for 2 h.
4. The method for preparing the supported NiPd bimetallic catalyst as described in claim 1, wherein (3) the graphene oxide aqueous solution is dropwise added into the materials dissolved in the step (1) to uniformly mix the materials; the dropping rate 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 is uniformly mixed with the sodium chloropalladate and the nickel chloride solution;
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: 50 mg;
preferably, in the step (3), the mass ratio of sodium chloropalladate to graphene oxide is 0.1 g: 50 mg.
5. The method for preparing a supported NiPd bimetallic catalyst as described in claim 1, wherein in the step (4), the mass-to-volume ratio of the sodium borohydride to the third part of deionized water is: (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: 0.993 g: 25 mL.
6. The process for preparing a supported NiPd bimetallic catalyst as claimed in claim 1, wherein in (5), the material obtained in (3) is placed in an oil bath to be heated while being magnetically stirred; the magnetic stirring speed is 1100-1300 r/min; gradually heating to 82-86 ℃ at the speed of 2-6 ℃/min during oil bath heating, dropwise adding the sodium borohydride solution in the step (4) within 20-40 min, continuously magnetically stirring for continuously reacting 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-to-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 1200 r/min; heating in an oil bath, gradually heating to 84 ℃ at the speed of 4 ℃/min, dropwise adding the sodium borohydride solution in the step (4) within 30min, keeping the solution in the oil bath at 84 ℃, magnetically stirring for continuously reacting for 3h, cooling to room temperature after the reaction is finished, and standing the obtained reaction solution for 12 h;
the volume-to-mass ratio of the sodium borohydride solution to the sodium chloropalladate is 1 mL: 0.1 g.
7. The preparation method of the supported NiPd bimetallic catalyst as described in claim 1, wherein (6) the reaction solution in (5) is centrifuged at 13000-15000 r/min for 15-25 min, washed with water and then washed with alcohol to obtain the supported NiPd bimetallic catalyst;
preferably, (6) centrifuging the reaction solution in the step (5) at the rotating speed of 13000-15000 r/min for 15-25 min, keeping the precipitate, washing the precipitate with deionized water for 3 times, and then washing the precipitate with absolute ethyl alcohol for 3 times; 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 20 min; and washing to obtain the supported NiPd bimetallic catalyst.
8. The method for preparing a supported NiPd bimetallic catalyst as recited in claim 1, further comprising (7) vacuum drying and milling the supported NiPd bimetallic catalyst obtained in (6) to obtain a 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 22-26 h under the temperature of 50-70 ℃, and the dried NiPd bimetallic catalyst is ground 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 24 hours in vacuum at 60 ℃, and the catalyst is ground to obtain the powdered supported NiPd bimetallic catalyst.
9. A process for the preparation of a supported NiPd bimetallic catalyst as claimed in claim 1, comprising the steps of:
(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: (0.025-0.028) 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 rate 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 is uniformly mixed with the sodium chloropalladate and the nickel chloride solution;
before mixing, the mass ratio of sodium chloropalladate to graphene oxide is (0.09-0.12) g: 50 mg;
(4) dissolving sodium borohydride in a 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; gradually heating to 82-86 ℃ at the speed of 2-6 ℃/min during oil bath heating, dropwise adding the sodium borohydride solution in the step (4) within 20-40 min, continuously magnetically stirring for continuously reacting 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-to-mass ratio of the sodium borohydride solution to the sodium chloropalladate is (0.9-1.1) mL: (0.08-0.12) g;
(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 the supported NiPd bimetallic catalyst.
10. Use of a supported NiPd bimetallic catalyst as in claim 1 in dehalogenation reactions.
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