CN104307512A - Supported palladium catalyst and preparation method and application thereof - Google Patents
Supported palladium catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a supported palladium catalyst and a preparation method and application thereof. The supported palladium catalyst disclosed by the invention comprises a graphene carrier and palladium nano-crystals or palladium nano-alloys supported on the carrier, wherein the palladium nano-crystals or palladium nano-alloys account for 10-50 mass percent. The preparation method comprises the following steps: (1) dissolving palladium salt in oleylamine to obtain a palladium salt solution, or dissolving cobalt salt or nickel salt and palladium salt in oleylamine to obtain a mixed solution; (2) adding a boron-nitrogen compound into the palladium salt solution or the mixed solution, and adding an organic settling agent, thereby obtaining the palladium nano-crystals or palladium nano-alloys; and (3) supporting the palladium nano-crystals or palladium nano-alloys on graphene, thereby obtaining the supported palladium catalyst. The supported palladium catalyst and the preparation method disclosed by the invention have the advantages that the preparation method is low in reaction temperature and is simple and convenient, and the shape and size of the palladium catalyst can be controlled. Moreover, the active ingredients of the supported palladium catalyst disclosed by the invention are uniform in size and high in dispersity, and the catalyst is high in activity and can be used for catalyzing formic acid oxidation.
Description
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Technical field
The present invention relates to a kind of load type palladium catalyst and its preparation method and application, belong to field of nanometer material technology.
Background technology
Nano material relies on the character-small-size effect of its uniqueness, surface and interface effect, quantum size effect and macroscopic quantum orbital effect etc., important using value is had at electronics, optics, chemical industry, pottery, biology and the numerous areas such as medical, therefore receive paying close attention to emphatically of countries in the world scientist, demonstrate huge application prospect simultaneously.Metal nano catalyst, as the important component part of nano material, has the advantages that specific area is large, effective active center density is high, to the efficiency, selective significant improving chemical reaction.In numerous metal nano catalyst, palladium metal nanocatalyst occupies critical role, but palladium metal reserves are rare, expensive, improve further its catalytic activity, selective, stability and utilization ratio is the great scientific issues of catalytic field and the technical problem of key project always.
The performance of metal nano catalyst can be passed through dimensional effect (reducing particle diameter, increasing specific surface area), carrier effect (improving dispersiveness and the stability of metal nanoparticle) and electronic structure effect (improving catalytic activity by the synergy of bimetallic or various metals) and carry out modulation.What is more important, because catalytic reaction occurs in catalyst surface, the surface texture of catalyst is the deciding factor of catalyst performance.Therefore, the catalytic activity of palladium metal, selective, stability and utilization ratio is improved mainly through regulation and control catalyst pattern and size at present.Wherein, electrochemical process and wet chemistry method are two kinds and prepare nanocrystalline common method.But electrochemical process output is relatively low, limit the batch production of palladium catalyst.It is also the best way that liquid phase synthesizing method in wet chemistry method is considered to the energy nanocrystalline pattern of accuracy controlling and the simplest of size at present.But the temperature of liquid phase method is very high (more than 160 DEG C), which also limits the application of palladium nanocatalyst.And the wet chemistry method comprising liquid phase synthesizing method will introduce the large molecule of stabilizing agent in building-up process, make it to poison because the large molecule of stabilizing agent can be adsorbed on prepared nanoparticle surface securely, thus seriously constrain the raising of its practical application and catalytic performance.
summary of the invention
The object of the invention is, for above-mentioned existing problems, to overcome the deficiencies in the prior art, a kind of load type palladium catalyst and its preparation method and application is provided.Preparation method provided by the invention can at room temperature carry out, and is conducive to realizing industrialization, and nanocrystalline size uniformity, morphology controllable, good dispersion in prepared catalyst, can produce in batches.
Object of the present invention is realized by following technical method:
A kind of load type palladium catalyst, comprise palladium nano-crystal or the palladium Nanoalloy of Graphene carrier and supported on carriers, the mass percent of described palladium nano-crystal or palladium Nanoalloy is 10%-50%.
Described palladium nano-crystal is one or both in palladium nanometer rods, palladium nano-particles, and described palladium Nanoalloy is palladium Nanoalloy particle.
Described palladium Nanoalloy is palladium cobalt Nanoalloy or palladium nickel Nanoalloy.
Prepare a method for above-mentioned load type palladium catalyst, comprise the steps:
(1) palladium salt is dissolved in oleyl amine, obtains the palladium salting liquid that concentration is 5-10 mmol/L, or
Be dissolved in oleyl amine by cobalt salt or nickel salt and palladium salt, the content forming palladium is the mixed solution of 5-10 mmol/L;
(2) add boron-nitrogen compound in the palladium salting liquid prepared in step (1) or mixed solution, at room temperature-90 DEG C, reaction 30-60 minute, then adds organic sedimentation agent, centrifugation, and washing is dry, obtains palladium nano-crystal or palladium Nanoalloy;
(3) palladium nano-crystal step (2) prepared or palladium Nanoalloy are dispersed in n-hexane, at room temperature add Graphene reaction, centrifugation, dry, obtain load type palladium catalyst.
The preparation method of described load type palladium catalyst, also comprises the steps: that the load type palladium catalyst by prepared by step (3) joins in glacial acetic acid solution, at 70 DEG C, stirs 6-12 hour.
Palladium salt in described step (1) is palladium bichloride, palladium or palladium acetylacetonate.
Cobalt salt in described step (1) is acetylacetone cobalt, cobalt chloride, cobaltous sulfate or cobalt acetate; Described nickel salt is nickel acetylacetonate, nickel chloride or nickelous sulfate.
The mol ratio of the cobalt salt in described mixed solution or nickel salt and palladium salt is 0.4-2:1.
Boron-nitrogen compound in described step (2) is 2-picoline borine, boron triethyl, N, N-diethylaniline borane, morphine borine, tert-butyl group borine or tri-n-butylbo-rane.
The mol ratio of the palladium salt in described boron-nitrogen compound and palladium salting liquid is 5-10:1.
The mol ratio of the cobalt salt in described boron-nitrogen compound and mixed solution or the total amount of nickel salt and palladium salt is 5-10:1.
Organic sedimentation agent in described step (2) is ethanol, isopropyl alcohol or acetone.
The application of above-mentioned load type palladium catalyst in oxidation formic acid.
A preferred embodiment of the present invention joins in acetum by load type palladium catalyst prepared by step (3), 6-12h is stirred at 70 DEG C, the large molecule that palladium nano-crystal or palladium Nanoalloy adsorb can be removed like this, eliminate its murder by poisoning to catalyst, thus improve the activity of catalyst.
Boron-nitrogen compound is traditional Lewis Acids and Bases pair, relative to traditional reducing agent metal boride, has many good qualities, as having adjustable dissolubility in proton and aprotic solvent; Reproducibility gentleness is controlled; Can regulate and control etc. its reproducibility by changing different substituents on boron or nitrogen.
Boron-nitrogen compound of the present invention is a general name, refers to boracic nitrogen or contains wherein a kind of compound.
In the present invention, we adopt liquid phase synthesizing method under oleyl amine system, regulate and control synthesis palladium nano-crystal.By the selection to palladium salt, reducing agent, palladium nanometer rods, the palladium nano-particles of different size and palladium Nanoalloy can be obtained.By the nanocrystalline load that obtains on Graphene, obtain load type palladium catalyst.Catalyst provided by the invention can Electrocatalytic Process for Oxidation of Formic Acid, and its catalytic effect is remarkable, and wherein graphene-supported palladium Nanorods Catalyst effect is best.
Preparation method provided by the invention is a kind of method of controllable palladium nano-crystal pattern and size.Wherein, obtain with N, N-diethylaniline borane reduction palladium acetylacetonate the nanometer rods that length is about 15 nm; With the mainly palladium nano-particles that N, N-diethylaniline borane reduction palladium bichloride obtains; What obtain with N, N-diethylaniline borane reduction acid chloride be the nano particle that diameter is about 5 nm is mixing of 10 nm nanometer rods with length; What obtain with 2-picoline borane reduction palladium acetylacetonate is mixing of 3.5 nm nano particles with diameter; With boron triethyl reduction, palladium acetylacetonate obtains is the nano particle that diameter is about 5.5 nm; Under oleyl amine system, with N, N-diethylaniline borane room temperature coreduction cobalt salt or nickel salt and palladium salt, centrifugation is dry, and the Pd-Co alloy obtained, palladium-nickel alloy are nano particle.Palladium nano-particles Monodispersed prepared by the present invention is even, size is less, and catalyst activity is increased greatly; Because the surface/volume value of nanometer rods is large, catalytic activity also strengthens to some extent; The alloy generated is due to synergy, and catalytic activity also significantly improves.Meanwhile, Graphene, as carrier, makes metal nanoparticle better to disperse, and effectively prevent the phenomenon that metallic assembles due to high surface energy, is conducive to recycling of catalyst.
In the present invention, the synthesis of catalyst have employed liquid-phase synthesis process, and namely under oleyl amine system, at room temperature reduce palladium salt with boron-nitrogen compound, the palladium nano-crystal spread loads obtained is on Graphene.Load type palladium nanocrystalline catalyst provided by the present invention can be used for the reaction of catalysis Oxidation of Formic Acid.Palladium nano-crystal catalyst of the present invention is brown-black powder solid, has particle little and homogeneous, and specific area is large, the feature that catalytic performance is good.
The pattern of the controlled palladium nano-crystal of preparation method provided by the invention and size, and at ambient temperature, the preparation of catalyst just can be completed, be conducive to the demand meeting industry.
Technical scheme of the present invention compared with prior art, has the following advantages and effect:
1. at room temperature just can realize the regulation and control of nanocrystalline pattern and size, be conducive to realizing industrialization;
2. need pattern and the size that just can regulate and control palladium nano-crystal or palladium Nanoalloy with boron-nitrogen compound as reducing agent;
3. the nanocrystalline size uniformity, morphology controllable, the good dispersion that obtain, can produce in batches;
4. preparation method of the present invention simple, convenient, be easy to operation, mild condition.
accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of palladium nanometer rods prepared by embodiment 3, and the multiplication factor wherein scheming (a) is 140000 times, and the multiplication factor of figure (b) is 670000 times.
Fig. 2 is the transmission electron microscope picture of graphene-supported palladium Nanorods Catalyst prepared by embodiment 3.
Fig. 3 is the transmission electron microscope picture of palladium nano-crystal prepared by embodiment 8, and the multiplication factor wherein scheming (a) is 190000 times, and the multiplication factor of figure (b) is 760000 times.
Fig. 4 is the transmission electron microscope picture of graphene-supported palladium nano-particles prepared by embodiment 8, and the multiplication factor wherein scheming (a) is 100000 times, and the multiplication factor of figure (b) is 430000 times.
Fig. 5 is the transmission electron microscope picture of palladium nano-crystal prepared by embodiment 9, and the multiplication factor wherein scheming (a) is 280000 times, and the multiplication factor of figure (b) is 670000 times.
Fig. 6 is the graphene-supported palladium nanometer rods of embodiment 9 preparation and the transmission electron microscope picture of nano particle, and the multiplication factor wherein scheming (a) is 140000 times, and the multiplication factor of figure (b) is 430000 times.
Fig. 7 is the transmission electron microscope picture of palladium nano-crystal prepared by embodiment 10, and the multiplication factor wherein scheming (a) is 140000 times, and the multiplication factor of figure (b) is 570000 times.
Fig. 8 is the transmission electron microscope picture of palladium nano-crystal prepared by embodiment 11, and the multiplication factor wherein scheming (a) is 190000 times, and the multiplication factor of figure (b) is 670000 times.
Fig. 9 is the transmission electron microscope picture of palladium cobalt Nanoalloy prepared by embodiment 15.
Figure 10 is the transmission electron microscope picture of palladium nickel Nanoalloy prepared by embodiment 19.
The cyclic voltammetry curve of the load type palladium nanocrystalline catalyst catalysis Oxidation of Formic Acid that Figure 11 is embodiment 3, prepared by embodiment 10, embodiment 11.
Detailed description of the invention
Embodiment 1
For the synthesis of palladium nanometer rods, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, injects 0.5 mmol N, N-diethylaniline borane, solution clearly become brownish black by colourless.Solution temperature is adjusted to 90 DEG C of reduction 30 minutes, drop to after room temperature until temperature, add ethanol and nano particle is settled down, centrifugation obtains nano particle.Then, wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder (palladium nano-crystal).Get powder 8 mg to be dispersed in 10 mL n-hexanes, add 72 mg Graphene, at room temperature loads, last centrifugation, drying, obtain load type palladium catalyst, and wherein the mass percentage content of palladium is 10%.
Embodiment 2
For the synthesis of palladium nanometer rods, be dissolved in by 0.1 mmol palladium acetylacetonate in 10 mL oleyl amines, by 0.8 mmol N, N-diethylaniline borane is injected in above-mentioned solution, solution clearly become brownish black by colourless.Solution temperature being adjusted to 50 DEG C of reduction obtains nanocrystalline in 45 minutes, and drop to after room temperature until temperature, add ethanol and nano particle is settled down, centrifugation obtains nano particle.Wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder (palladium nano-crystal).Get 8 mg powder dispersion in 10 mL n-hexanes, add 32 mg Graphene, at room temperature loads, last centrifugation, drying, obtain load type palladium catalyst, and wherein the mass percentage content of palladium is 20%.
Embodiment 3
For the synthesis of palladium nanometer rods, be dissolved in by 0.1 mmol palladium acetylacetonate in 10 mL oleyl amines, by 1 mmol N, N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, at room temperature react 1 hour.Adding ethanol subsequently makes nano particle settle down, and centrifugation obtains nano particle.Nano particle, drying is washed successively with distilled water and ethanol, obtain brown-black powder (palladium nano-crystal), its transmission electron microscope picture as shown in Figure 1, as can be seen from the figure prepared nano particle is nanometer rods, its size uniformity, good dispersion, clearly can see the lattice fringe of palladium from Fig. 1 (b), its spacing of lattice is about 0.23nm, corresponding with (111) crystal face of palladium.Get 8 mg powder dispersion in 10 mL n-hexanes, add Graphene 8 mg, at room temperature load, centrifugation, drying.Finally join in glacial acetic acid solution by dried material, 70 DEG C are stirred centrifugations after 6 hours, and use water and ethanol washing catalyst, drying successively, obtain load type palladium catalyst, wherein, the load quality percentage of palladium is 50%.As shown in Figure 2, the pattern of the palladium nanometer rods as can be seen from the figure after load is not destroyed its transmission electron microscope picture, and its favorable dispersibility.
Embodiment 4
For the synthesis of palladium nanometer rods, 0.05 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, 0.5 mmol N, N-diethylaniline borane is injected in solution, solution clearly becomes brownish black by colourless, react 1 hour under room temperature, add ethanol subsequently and nano particle is settled down, centrifugation obtains nano particle.Then, wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.By 4 mg powder dispersion in 10 mL n-hexanes, add 16 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 5
For the synthesis of palladium nanometer rods, 0.08 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, 0.8 mmol N, N-diethylaniline borane is injected in solution, solution clearly becomes brownish black by colourless, react 1 hour under room temperature, add ethanol subsequently and nano particle is settled down, centrifugation obtains nano particle.Then wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 6
For the synthesis of palladium nanometer rods, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, 1 mmol N, N-diethylaniline borane is injected in solution, solution clearly becomes brownish black by colourless, react 1 hour under room temperature, add isopropyl alcohol subsequently and nano particle is settled down, centrifugation obtains nano particle.Then wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 7
For the synthesis of palladium nanometer rods, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, 1 mmol N, N-diethylaniline borane is injected in solution, solution clearly becomes brownish black by colourless, react 1 hour under room temperature, add acetone subsequently and nano particle is settled down, centrifugation obtains nano particle.Then, wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 8
Synthesize palladium nano-particles for palladium bichloride, 0.1 mmol palladium bichloride is dissolved in 10 mL oleyl amines, 1 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless.React 1 hour under room temperature, add a large amount of ethanol and nano particle is settled down, the nano particle obtained obtains through centrifugation.Then, brown-black powder is obtained successively with distilled water and ethanol washing nano particle, drying, its transmission electron microscope picture as shown in Figure 3, as can be seen from the figure prepared nano particle is nano particle, its size uniformity, good dispersion, clearly can see the lattice fringe of palladium from Fig. 3 (b), its spacing of lattice is about 0.23nm, corresponding with (111) crystal face of palladium.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphenes, at room temperature load, centrifugation, drying, obtain load type palladium catalyst, as shown in Figure 4, the pattern of the palladium nano-particles as can be seen from the figure after load is not destroyed its transmission electron microscope picture, and its favorable dispersibility.
Embodiment 9
For with palladium synthesis palladium nano-particles and nanometer rods, 0.1 mmol palladium is dissolved in 10 mL oleyl amines, 1 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless.React 1 hour under room temperature, add a large amount of ethanol and nano particle is settled down, centrifugation obtains nano particle.Then, obtain brown-black powder with distilled water and ethanol washing nano particle, drying successively, as shown in Figure 5, the as can be seen from the figure prepared existing nano particle of nano particle has nanometer rods again to its transmission electron microscope picture, and good dispersion; Can see the lattice fringe of palladium from Fig. 5 (b) clearly, its spacing of lattice is about 0.23nm, corresponding with (111) crystal face of palladium.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphenes, at room temperature load, centrifugation, drying, obtain load type palladium catalyst, as shown in Figure 6, the pattern of the Pd nano particle as can be seen from the figure after load is not destroyed its transmission electron microscope picture, and its favorable dispersibility.
Embodiment 10
For with 2-picoline borane reduction palladium acetylacetonate synthesis palladium nano-particles method, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, and 1 mmol 2-picoline borine is injected in solution, solution clearly become brownish black by colourless.React 1 hour under room temperature, add a large amount of ethanol and nano particle is settled down, centrifugation obtains nano particle.Then nano particle, drying is washed with distilled water and ethanol successively, obtain brown-black powder, its transmission electron microscope picture as shown in Figure 7, as can be seen from the figure prepared nano particle is nano particle, its size uniformity, good dispersion, can clearly see its lattice fringe from Fig. 7 (b), its spacing of lattice is about 0.23nm, corresponding with (111) crystal face of palladium.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, finally join in glacial acetic acid solution by the solid obtained, 70 DEG C are stirred centrifugations after 8 hours, use water and ethanol washing catalyst, drying successively.Obtain load type palladium catalyst.
Embodiment 11
For with boron triethyl reduction synthesis palladium nano-particles, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, and 1 mmol boron triethyl is injected in solution, solution clearly become brownish black by colourless, react 1 hour under room temperature.Adding a large amount of ethanol makes nano particle settle down, and nano particle centrifugation obtains.Then, wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder, as shown in Figure 8, as can be seen from the figure prepared nano particle is nano particle to its transmission electron microscope picture, its size uniformity, good dispersion, and its diameter is about 5.5 nm; Clearly can see the lattice fringe of palladium from Fig. 8 (b), its spacing of lattice is about 0.23nm, corresponding with (111) crystal face of palladium.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphenes, at room temperature load, centrifugation, drying, obtain solid, finally join in glacial acetic acid solution by the solid obtained, 70 DEG C are stirred centrifugation after 12 hours, use water and ethanol washing catalyst, drying successively, obtain load type palladium catalyst.
Embodiment 12
For with morphine borane reduction synthesis palladium nano-particles, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, and 1 mmol morphine borine is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then brown-black powder is obtained with distilled water and ethanol washing nano particle, drying successively.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 13
For with the tert-butyl group borane reduction synthesis palladium nano-particles, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, and 1 mmol tert-butyl group borine is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 14
For with tri-n-butylbo-rane reduction synthesis palladium nano-particles, 0.1 mmol palladium acetylacetonate is dissolved in 10 mL oleyl amines, and 1 mmol tri-n-butylbo-rane is injected in solution, solution clearly become brownish black by colourless, react 1 hour under room temperature.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then, wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium catalyst.
Embodiment 15
For the synthesis of Pd-Co alloy, 0.05 mmol palladium acetylacetonate and 0.05 mmol acetylacetone cobalt are dissolved in 10 mL oleyl amines, 1 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then, successively with distilled water and ethanol washing nano particle, dry, obtain brown-black powder, as shown in Figure 9, as can be seen from the figure prepared nano particle is nano particle to its transmission electron microscope picture, its size uniformity, good dispersion.Get 5 mg powder dispersion in 10 mL n-hexanes, add 45 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Co catalysts, wherein the mass percent of Pd-Co alloy is 10%.
Embodiment 16
For the synthesis of Pd-Co alloy, 0.1 mmol palladium acetylacetonate and 0.04 mmol cobalt chloride are dissolved in 10 mL oleyl amines, 1.12 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then successively with distilled water and ethanol washing nano particle, dry, obtain brown-black powder.Get powder 5 mg to be dispersed in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Co catalysts, wherein the mass percent of Pd-Co alloy is 20%.
Embodiment 17
For the synthesis of Pd-Co alloy, 0.06 mmol palladium acetylacetonate and 0.12mmol cobaltous sulfate are dissolved in 10 mL oleyl amines, 0.9 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then, wash nano particle, drying with distilled water and ethanol successively, obtain brown-black powder.Get 8 mg powder dispersion in 10 mL n-hexanes, add 8 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Co catalysts, wherein the mass percent of Pd-Co alloy is 50%.
Embodiment 18
For the synthesis of Pd-Co alloy, 0.05 mmol palladium acetylacetonate and 0.05 mmol cobalt acetate are dissolved in 10 mL oleyl amines, 1 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then successively with distilled water and ethanol washing nano particle, dry, obtain brown-black powder.By 5 mg powder dispersion in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Co catalysts.
Embodiment 19
For the synthesis of palladium-nickel alloy, 0.05 mmol palladium acetylacetonate and 0.05 mmol nickel acetylacetonate are dissolved in 10 mL oleyl amines, 1 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then successively with distilled water and ethanol washing, dry, obtain brown-black powder, as shown in Figure 10, nano particle prepared is as we can see from the figure nano particle to its transmission electron microscope picture, its size uniformity, good dispersion.Get 5 mg powder dispersion in 10 mL n-hexanes, add 45 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Raney nickel, wherein the mass percent of palladium-nickel alloy is 10%.
Embodiment 20
For the synthesis of palladium-nickel alloy, 0.1 mmol palladium acetylacetonate and 0.04 mmol nickel chloride are dissolved in 10 mL oleyl amines, 1.12 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then successively with distilled water and ethanol washing, nano particle is dry, obtains brown-black powder.Get powder 5 mg to be dispersed in 10 mL n-hexanes, add 20 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Raney nickel, wherein the mass percent of palladium-nickel alloy is 20%.
Embodiment 21
For the synthesis of palladium-nickel alloy, 0.06 mmol palladium acetylacetonate and 0.12mmol nickelous sulfate are dissolved in 10 mL oleyl amines, 0.9 mmol N, and N-diethylaniline borane is injected in solution, solution clearly become brownish black by colourless, under room temperature react 1 hour.Adding a large amount of ethanol makes nano particle settle down, and centrifugation obtains nano particle.Then successively with distilled water and ethanol washing nano particle, dry, to brown-black powder.8 mg powder dispersion, in 10 mL n-hexanes, add 8 mg Graphene, at room temperature loads, centrifugation, drying, obtain load type palladium Raney nickel, and wherein the mass percent of palladium-nickel alloy is 50%.
Catalysis Oxidation of Formic Acid is tested
The graphene-supported palladium catalyst prepare embodiment 3, embodiment 10, embodiment 11 and the business palladium catalyst of carbon load are dispersed in water the concentration 2.5 mg/mL suspension forming catalyst respectively, pipette 10 μ L suspension to glassy carbon electrode surface, after drying, obtain working electrode.Be to electrode with platinized platinum, take saturated calomel electrode as reference electrode, three electrodes are put in the mixed solution (wherein the concentration of perchloric acid is 0.1mol/L, and the concentration of formic acid is 2 mol/L) of perchloric acid and formic acid, measure its current density under different potentials.Its cyclic voltammetry curve as shown in figure 11, shows high catalytic activity with the load type palladium nanocrystalline catalyst of boron-nitrogen compound reduction preparation to Oxidation of Formic Acid as we know from the figure.The catalyst being active component with palladium nanometer rods shows best catalytic effect, and its catalytic activity is 2 times of business palladium carbon.
Claims (10)
1. a load type palladium catalyst, is characterized in that: the palladium nano-crystal or the palladium Nanoalloy that comprise Graphene carrier and supported on carriers, and the mass percent of described palladium nano-crystal or palladium Nanoalloy is 10%-50%.
2. a kind of load type palladium catalyst according to claim 1, is characterized in that: described palladium nano-crystal is one or both in palladium nanometer rods, palladium nano-particles, and described palladium Nanoalloy is palladium Nanoalloy particle; Described palladium Nanoalloy is palladium cobalt Nanoalloy or palladium nickel Nanoalloy.
3. prepare a method for load type palladium catalyst described in claim 1 or 2, it is characterized in that comprising the steps:
(1) palladium salt is dissolved in oleyl amine, obtains the palladium salting liquid that concentration is 5-10 mmol/L, or
Be dissolved in oleyl amine by cobalt salt or nickel salt and palladium salt, the content forming palladium is the mixed solution of 5-10 mmol/L;
(2) add boron-nitrogen compound in the palladium salting liquid prepared in step (1) or mixed solution, at room temperature-90 DEG C, reaction 30-60 minute, then adds organic sedimentation agent, centrifugation, and washing is dry, obtains palladium nano-crystal or palladium Nanoalloy;
(3) palladium nano-crystal step (2) prepared or palladium Nanoalloy are dispersed in n-hexane, at room temperature add Graphene reaction, centrifugation, dry, obtain load type palladium catalyst.
4. the preparation method of a kind of load type palladium catalyst according to claim 3, it is characterized in that: the preparation method of described load type palladium catalyst, also comprise the steps: that the load type palladium catalyst by prepared by step (3) joins in glacial acetic acid solution, at 70 DEG C, stir 6-12 hour.
5. a kind of preparation method of load type palladium catalyst according to claim 3 or 4, is characterized in that: the palladium salt in described step (1) is palladium bichloride, palladium or palladium acetylacetonate; Cobalt salt is acetylacetone cobalt, cobalt chloride, cobaltous sulfate or cobalt acetate; Nickel salt is nickel acetylacetonate, nickel chloride or nickelous sulfate.
6. a kind of preparation method of load type palladium catalyst according to claim 3 or 4, is characterized in that: the mol ratio of the cobalt salt in described mixed solution or nickel salt and palladium salt is 0.4-2:1.
7. a kind of preparation method of load type palladium catalyst according to claim 3 or 4, it is characterized in that: the boron-nitrogen compound in described step (2) is 2-picoline borine, boron triethyl, N, N-diethylaniline borane, morphine borine, tert-butyl group borine or tri-n-butylbo-rane; Organic sedimentation agent is ethanol, isopropyl alcohol or acetone.
8. a kind of preparation method of load type palladium catalyst according to claim 3 or 4, is characterized in that: the mol ratio of the palladium salt in described boron-nitrogen compound and palladium salting liquid is 5-10:1.
9. a kind of preparation method of load type palladium catalyst according to claim 3 or 4, is characterized in that: the mol ratio of the cobalt salt in described boron-nitrogen compound and mixed solution or the total amount of nickel salt and palladium salt is 5-10:1.
10. the application of the load type palladium catalyst described in claim 1 or 2 in oxidation formic acid.
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