CN111804291A - Small-size Pd3Pb intermetallic compound and preparation method and application thereof - Google Patents
Small-size Pd3Pb intermetallic compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN111804291A CN111804291A CN202010699630.8A CN202010699630A CN111804291A CN 111804291 A CN111804291 A CN 111804291A CN 202010699630 A CN202010699630 A CN 202010699630A CN 111804291 A CN111804291 A CN 111804291A
- Authority
- CN
- China
- Prior art keywords
- intermetallic compound
- carbon
- palladium
- carbon carrier
- heat treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 230000007547 defect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 108
- 238000010438 heat treatment Methods 0.000 claims description 38
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002113 nanodiamond Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 150000004682 monohydrates Chemical class 0.000 claims 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000012876 carrier material Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 229910003460 diamond Inorganic materials 0.000 abstract description 2
- 239000010432 diamond Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 5
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000011981 lindlar catalyst Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 palladium monohydrate Chemical class 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003887 surface segregation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a small-size Pd3Pb intermetallic compound, Pd supported by defect structure-containing carbon carrier3The Pb metal is prepared, the carbon carrier containing the defect structure is carbon with an sp3 structure as an inner layer, and the carbon carrier containing the defect structure is provided with an outer layerOne to two layers of a core-shell structure of sp2 structured carbon. According to the invention, the carbon carrier with the core-shell structure, the outer surface of which is wrapped by two graphite carbon layers rich in a large number of defects, is obtained by carrying out high-temperature treatment on the diamond carbon carrier. The carbon carrier material has strong confinement effect and electron supply characteristic on metal, and enables the metal to have strong anti-sintering performance at high temperature without adding any protective agent and coating agent. The invention utilizes the confinement effect of the carrier to overcome the sintering of metal at high temperature, and uses the common metal salt precursor to realize the Pd with small size and high order3And preparing a Pb intermetallic compound. The process is simple and easy to operate, is easy for mass preparation, and has a good application prospect in the semi-hydrogenation reaction of alkyne.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to small-size Pd3Pb intermetallic compound and its preparation method and application.
Background
The supported palladium-based catalyst has important industrial application in hydrogenation reaction due to the unique electronic structure and geometric structure. However, due to the excellent catalytic activity of the catalyst, the catalyst is easy to cause low selectivity in selective hydrogenation reaction, and particularly, the catalyst is often excessively hydrogenated in semi-hydrogenation reaction of alkyne. The activity of the beta-PdH (beta-H) species formed on the subsurface of the single-metal Pd particles is very high, and the beta-PdH (beta-H) species is one of the main reasons for excessive hydrogenation of alkyne.
Not only can Pd atoms be diluted by embedding a second metal into Pd crystal lattice alloying action, thereby inhibiting the generation of beta-H species; and the electronic structure at the Fermi level can be adjusted, the adsorption capacity to double bonds is reduced, and the selectivity of olefin is improved. In the traditional Pd-based alloy catalyst, two metal components are arranged in a disordered form, so that Pd atoms are difficult to completely separate; moreover, the alloy catalyst is easy to generate surface segregation phenomenon under high temperature condition, and the adsorption capacity of the alloy catalyst to olefin is difficult to control. The highly ordered Pd-based intermetallic compound has a specific geometric/electronic structure and uniform active sites, and can perfectly compensate for these disadvantages of the disordered alloy.
However, most Pd-based intermetallic compounds are prepared under high-temperature reduction, and tend to sinter and grow into larger metal particles at high temperature due to the unstable characteristic of Pd itself. Thus the synthetic particle diameter<5nm Pd3Pb intermetallics still face significant challenges. Larger metal nanoparticles tend to result in lower utilization of Pd atoms, which undoubtedly increases the production cost of enterprises.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a small Pd3Pb intermetallic compound, preparation method and application thereof, and prepared Pd3The average particle size of the Pb intermetallic compound is less than 5 nm.
The invention provides a small-size Pd3Pb intermetallic compound, Pd supported by defect structure-containing carbon carrier3And preparing Pb metal, wherein the carbon carrier containing the defect structure is a core-shell structure with an inner layer of sp3 structure carbon and an outer layer of one to two layers of sp2 structure carbon.
The Pd3The metal atoms in the Pb intermetallic compound and the carbon carrier have strong electron interaction, so that the sintering growth of metal particles under the high-temperature condition can be well inhibited, and the stability and the atom utilization rate of the catalyst are greatly improved.
Based on the structure, the material provided by the invention has a long-range ordered structure and a specific electronic structure and a specific geometric structure, so that the effective utilization of palladium atoms is greatly increased, and meanwhile, the material provides potential application for specific selective catalytic reaction.
Preferably, the carbon support containing the defect structure is prepared according to the following method:
and carrying out heat treatment on the nano-diamond to obtain the carbon carrier with the surface containing the defect structure.
C of the nano-diamond belongs to an sp3 structure, and after high-temperature heat treatment, the outer layer is converted into a shell structure formed by one to two layers of sp2 structure carbon.
The source of the nanodiamond in the present invention is not particularly limited, and may be generally commercially available. The particle size of the nano-diamond is preferably 10-30 nm.
The temperature of the heat treatment is preferably 600-1000 ℃, more preferably 700-1000 ℃, and further preferably 800-1000 ℃; the lower limit of the heat treatment temperature is preferably 650, 700, 750 or 800 ℃; the upper limit of the temperature of the heat treatment is preferably 850, 900, 950, 1000 ℃; in some embodiments of the invention, the temperature of the heat treatment is 900 ℃.
The time of the heat treatment is preferably 1-12 h, more preferably 2-12 h, further preferably 2-8 h, and further preferably 2-6 h; the lower limit of the time of the heat treatment is preferably 1.5, 2, 2.5, 3, 3.5 and 4 hours; the upper limit of the time of the heat treatment is preferably 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 h. In some embodiments of the invention, the heat treatment time is 4 hours.
The heating rate of the heat treatment is preferably 1 to 20 ℃/min, more preferably 2 to 10 ℃/min, and even more preferably 3 to 8 ℃/min, and in some embodiments of the present invention, the heating rate of the heat treatment is 5 ℃/min.
The carrier prepared by the invention can show extremely stable anchoring effect on metal through the confinement effect on the metal and strong electron interaction, thereby solving the problem that Pd particles are easy to sinter, and the loaded Pd3The average particle diameter of Pb metal is 5nm or less.
The Pd3The loading amount of Pb metal is preferably 1 to 7 wt%, more preferably 2 to 6 wt%.
The present invention provides the above-mentioned small-sized Pd3A method for producing a Pb intermetallic compound, comprising the steps of:
A) carrying out heat treatment on the nano-diamond to obtain a carbon carrier with a surface containing a defect structure;
B) uniformly mixing the carbon carrier obtained in the step A) with a palladium-containing precursor and a lead-containing precursor in a solution, and drying to obtain a dry powder mixture;
C) reducing the dry powder mixture at high temperature in a hydrogen atmosphere to obtain small-size Pd3A Pb intermetallic compound.
The conditions of the step A) heat treatment are the same as above, and are not described again.
Preferably, the heat treatment is carried out in an inert atmosphere. The inert gas atmosphere in the present invention is not particularly limited, and may be a general inert gas known to those skilled in the art. The present invention is preferably one or more of nitrogen, argon and helium.
The flow rate of the inert gas is preferably 10-100 mL/min.
In some embodiments of the invention, the heat treatment is in particular:
and (3) placing the nano-diamond into a crucible, placing the crucible into a tubular furnace, and carrying out heat treatment.
The carbon carrier containing a defect structure is obtained after the nano diamond is subjected to heat treatment, and is marked as ND @ G. The carbon carrier is of a core-shell structure, the inner layer is carbon with an sp3 structure, and the outer layer comprises one to two layers of carbon with an sp2 structure.
And then uniformly mixing the carbon carrier, a palladium-containing precursor and a lead-containing precursor in a solution, and drying to obtain a dry powder mixture.
In the present invention, the palladium-containing precursor is a metal salt of palladium, preferably one or more selected from palladium chloride, dichlorodiammine palladium, ammonium chloropalladate, dichlorotetraammine palladium monohydrate, palladium (II) nitrate dihydrate, potassium chloropalladate, bis (acetylacetonato) palladium (II), and palladium acetate.
The lead-containing precursor is a metal salt of lead, preferably one or more selected from lead nitrate and lead acetate.
The molar ratio of Pd in the palladium-containing precursor to pb in the lead-containing precursor is preferably about 3: 1.
The solvent of the solution is not particularly limited, and a conventional solvent such as ethanol, water and the like can be selected according to the solubility of the palladium-containing precursor and the lead-containing precursor.
The method of mixing in the present invention is not particularly limited, and may be a general mixing method known to those skilled in the art, such as stirring, sonication, and the like.
In some embodiments of the invention, the mixing is in particular:
mixing a carbon carrier with a palladium-containing precursor and a lead-containing precursor in a solution, performing ultrasonic treatment, and then violently stirring;
the ultrasonic time is preferably more than 1 hour, and more preferably 1-3 hours; the time for vigorous stirring is preferably more than 24 hours, and more preferably 24-72 hours.
The method of drying is not particularly limited in the present invention, and may be a general method of drying a solution, which is well known to those skilled in the art.
The present invention preferably adopts a rotary evaporation method.
Finally, reducing the dry powder mixture at high temperature in a hydrogen atmosphere to obtain the small-size Pd3Pb intermetallic compound
The hydrogen atmosphere preferably includes hydrogen and either or both of argon and nitrogen.
The volume content of the hydrogen gas is preferably 3% to 10%, more preferably 3% to 5%.
More preferably, H with the hydrogen volume content of 3-5 percent2/Ar or H2/N2And (4) mixing the gases.
The gas flow rate of the hydrogen atmosphere is preferably 50-100 mL/min.
The temperature of the high-temperature reduction is 500-750 ℃; more preferably 500 to 700 ℃. The lower limit of the high-temperature reduction temperature is preferably 500, 550 and 600 ℃; the upper limit of the high-temperature reduction temperature is preferably 650, 700, 750 ℃.
The high-temperature reduction time is 1-6 h; more preferably 2 to 5 hours.
The temperature rise rate of the high-temperature reduction is 1-20 ℃/min, more preferably 1-10 ℃/min, and still more preferably 5-10 ℃/min.
The Pd can be prepared by a simple impregnation method and high-temperature reduction3The Pb intermetallic compound enables the metal particles to show excellent sintering resistance at high temperatures by the confinement effect of the carrier on the metal. The method is simple and easy to operate, and is easy for expanded production.
The present invention provides the above-mentioned small-sized Pd3Pb intermetallic compound, or small-sized Pd produced by the above production method3Pb intermetallic compound is used as catalyst for selective hydrogenation of alkyne.
The experimental result shows that the small-size Pd provided by the invention3The Pb intermetallic compound has good catalytic activity in the semi-hydrogenation reaction of alkyne.
Compared with the prior art, the invention provides a small-size Pd3Pb intermetallic compound, Pd supported by defect structure-containing carbon carrier3Pb goldThe carbon carrier containing the defect structure is prepared by a core-shell structure with an inner layer of sp3 structure carbon and an outer layer of one to two layers of sp2 structure carbon. According to the invention, the carbon carrier with the core-shell structure, the outer surface of which is wrapped by two graphite carbon layers rich in a large number of defects, is obtained by carrying out high-temperature treatment on the diamond carbon carrier. The carbon carrier material has strong confinement effect and electron supply characteristic on metal, and enables the metal to have strong anti-sintering performance at high temperature without adding any protective agent and coating agent. The invention utilizes the confinement effect of the carrier to overcome the sintering of metal at high temperature, and uses the common metal salt precursor to realize the Pd with small size and high order3And preparing a Pb intermetallic compound. The process is simple and easy to operate, is easy for mass preparation, and has a good application prospect in the semi-hydrogenation reaction of alkyne.
Drawings
FIG. 1 is a graph showing a nitrogen adsorption/desorption curve and a pore size distribution of ND @ G prepared in example 1 of the present invention and an OLC carrier prepared in comparative example 1;
FIG. 2 is an electron micrograph of a high-angle annular dark field image-scanning transmission electron microscope (HAADF-STEM) of Pd particles obtained by treating Pd on an ND @ G carrier at different reduction temperatures according to example 2 of the present invention and a corresponding particle size distribution diagram;
FIG. 3 shows Pd provided in example 3 of the present invention3HAADF-STEM electron micrographs, XRD, spherical aberration electron micrographs and energy dispersive spectroscopy mapping (EDS-mapping) pictures of the Pb intermetallic compound material;
FIG. 4 shows Pd as provided in comparative example 2 of the present invention3HAADF-STEM electron micrograph and particle size distribution map of Pb;
FIG. 5 shows Pd as provided in comparative example 3 of the present invention3HAADF-STEM electron micrograph and particle size distribution map of Pb;
FIG. 6 shows Pd provided in example 3 of the present invention and comparative examples 1 to 23Pd in Pd3X-ray photoelectron spectroscopy (XPS) of d;
FIG. 7 is a graph showing the results of selective hydrogenation catalytic performance of phenylacetylene in example 4 of the present invention.
Detailed Description
To is coming toFurther illustrating the invention, the following examples are given to provide the small size Pd3The Pb intermetallic compound and the preparation method and application thereof are described in detail.
Example 1
And (3) putting 1G of the raw material ND into a crucible, transferring the crucible into a tubular furnace, heating to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon, and carrying out heat treatment for 4 hours to obtain the carbon carrier containing the defect structure, wherein the mark is ND @ G.
Comparative example 1
And (2) putting 1g of the raw material ND into a crucible, transferring the crucible into a tube furnace, heating to 1100 ℃ at the heating rate of 5 ℃/min under the protection of argon, and carrying out heat treatment for 12 hours to obtain the carbon carrier with the onion structure, wherein the carbon carrier is marked as OLC.
Fig. 1 shows nitrogen adsorption-desorption curves (left) and a pore size distribution diagram (right) of ND @ G provided in example 1 of the present invention and OLC provided in comparative example 1.
As can be seen from FIG. 1, the specific surface area of the ND @ G carrier was 365m2(ii)/g, specific surface area of OLC support resulting in multilayer graphene structure at higher temperature (475 m)2/g) is increased, but the pore size distribution is hardly affected at high temperatures.
Example 2
50mg of ND @ G prepared in example 1 above was mixed with a palladium chloride solution containing 1.5mg of Pd and diluted with water so that the total volume of the mixed solution was kept at 40 mL. And (3) carrying out ultrasonic treatment on the obtained mixed solution for 1h, and then stirring at room temperature for 24 h to ensure that the precursor and the carbon carrier are fully and uniformly mixed. And carrying out rotary evaporation on the mixed solution to obtain a dry powder mixture, transferring the mixture into a quartz boat, reducing the mixture in 5 vol% hydrogen/argon mixed gas, controlling the heating rate at 5-10 ℃/min, respectively heating to 300 ℃, 500 ℃, 650 and 750 ℃, preserving heat for 2h, and then naturally cooling to room temperature.
FIG. 2 is a HAADF-STEM picture and a corresponding particle size distribution diagram provided in example 2 of the present invention.
It can be seen that Pd was obtained at 300, 500, 650 and 750 ℃ reduction temperatures3The grain sizes of the Pb intermetallic compound are respectively 1.7 nm, 2.9 nm, 4.6 nm and 5.7 nm,exhibits excellent sintering resistance.
Example 3
50.0mg of each of ND @ G and OLC prepared in example 1 and commercial carbon black Vulcan XC-72R (XC) were mixed with a palladium chloride solution containing 1.5mg of Pd, a lead nitrate solution was further added so that the atomic ratio of Pd to Pb was 3:1, and finally water was added for dilution so that the total volume of the mixed solution was kept at 40 mL. And (3) carrying out ultrasonic treatment on the obtained mixed solution for 1h, and then stirring at room temperature for 24 h to ensure that the precursor and the carbon carrier are fully and uniformly mixed. And carrying out rotary evaporation on the mixed solution to obtain a dry powder mixture, transferring the mixture into a quartz boat, reducing the mixture in 5 vol% hydrogen/argon mixed gas, controlling the heating rate at 5-10 ℃/min, heating to 650 ℃, and preserving heat for 2 h. Then naturally cooling to room temperature to obtain Pd3A Pb intermetallic compound.
FIG. 3 is Pd provided in example 3 of the present invention3XRD of Pb intermetallic compound (FIG. a), HA ADF-STEM (FIG. b), spherical aberration electron microscope picture (FIG. c) and corresponding EDS mapping picture (FIG. d).
Pd can be seen from the HAADF-STEM diagram3The Pb particles were uniformly distributed on the carbon carrier, and the presence of large particles was not observed, and it can be seen from the EDS-mapping chart that Pd and Pb were uniformly distributed in the particles.
Comparative example 2
50.0mg of the OLC prepared in example 1 was mixed with a palladium chloride solution containing 1.5mg of Pd, and then a lead nitrate solution was added thereto so that the atomic ratio of Pd to Pb was 3:1, and finally diluted with water so that the total volume of the mixed solution was kept at 40 mL. The procedure of example 3 was followed to obtain OLC-supported Pd3A Pb intermetallic compound.
FIG. 4 shows Pd as provided in comparative example 2 of the present invention3HAADF-STEM picture of Pb intermetallic compound and corresponding particle size distribution. Pd prepared on OLC can be seen from HAADF-STEM graph3The particles of the Pb intermetallic compound are not uniform in size, and the average particle size reaches 6.5 nm.
Comparative example 3
Commercial carbon black Vulcan XC-72R (XC) was mixed with a palladium chloride solution containing 1.5mgPd, and a lead nitrate solution was further added so that the atomic ratio of Pd and Pb was 31, finally adding water for dilution so as to keep the total volume of the mixed solution at 40 mL. Following the procedure of example 3, XC-supported Pd was obtained3A Pb intermetallic compound.
FIG. 5 is Pd produced in comparative example 3 of the present invention3HAADF-STEM picture of Pb intermetallic compound and corresponding particle size distribution. Pd prepared on OLC can be seen from HAADF-STEM graph3The particle size of the Pb intermetallic compound is very uneven, and the average particle size reaches 7.2 nm.
FIG. 6 shows Pd as provided in example 3 of the present invention and comparative examples 1 to 23Pd in Pb intermetallic compound3d XPS spectrum. Pd3Pd electrons in the Pb/ND @ G catalyst are shifted to the direction of lower electron binding energy by 1.4eV, which shows that ND @ G has extremely strong electron transfer function on metal. And Pd on both OLC and XC supports3The most part of Pd in the Pb intermetallic compound is in a metallic state, and the surface is partially oxidized.
Example 4
Pd prepared in example 33Pb intermetallic Compound for Selective hydrogenation reaction of Phenylacetylene hydrogenation Using Pd prepared in comparative examples 2 and 33Pb, commercial Lindlar catalyst, support ND @ G for comparison. Reaction conditions are as follows: 1mmol of substrate, 0.1 mol% Pd, a reaction pressure of 3bar and a temperature of 25 ℃.
FIG. 7 shows the catalytic performance test of phenylacetylene semi-hydrogenation reaction and Pd3Kinetic test chart of phenylacetylene hydrogenation reaction of Pb/ND @ G. Pd supported on ND @ G carbon support can be seen in FIG. 73The activity of the Pb catalyst is higher than that of Pd supported on OLC and XC carriers3The catalytic activity of Pb is much higher, and the carrier ND @ G is almost inactive under the same conditions. Not only that, Pd3The activity of the Pb/ND @ G catalyst is three times that of the commercial Lindlar catalyst, and the selectivity is still over 90% under the condition of complete substrate conversion, thereby showing good activity and selectivity.
As can be seen from the above examples and comparative examples, the small-sized Pd prepared by the present invention3The Pb intermetallic compound has uniform grain diameter and higher catalytic activity.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. Small-size Pd3Pb intermetallic compound, Pd supported by defect structure-containing carbon carrier3And preparing Pb metal, wherein the carbon carrier containing the defect structure is a core-shell structure with an inner layer of sp3 structure carbon and an outer layer of one to two layers of sp2 structure carbon.
2. Small size Pd according to claim 13A Pb intermetallic compound, characterized in that the defect structure-containing carbon support is prepared according to the following method:
and carrying out heat treatment on the nano-diamond to obtain the carbon carrier with the surface containing the defect structure.
3. Small size Pd according to claim 23The Pb intermetallic compound is characterized in that the heat treatment temperature is 600-1000 ℃;
the heat treatment time is 1-12 h;
the temperature rise speed of the heat treatment is 1-20 ℃/min.
4. Small-size Pd3A method for producing a Pb intermetallic compound, comprising the steps of:
A) carrying out heat treatment on the nano-diamond to obtain a carbon carrier with a surface containing a defect structure;
B) uniformly mixing the carbon carrier obtained in the step A) with a palladium-containing precursor and a lead-containing precursor in a solution, and drying to obtain a dry powder mixture;
C) reducing the dry powder mixture at high temperature in a hydrogen atmosphere to obtain small-size Pd3A Pb intermetallic compound.
5. The method according to claim 4, wherein the heat treatment temperature is 600 to 1000 ℃;
the heat treatment time is 1-12 h;
the temperature rise speed of the heat treatment is 1-20 ℃/min.
6. The preparation method according to claim 2, wherein the palladium-containing precursor is one or more of palladium chloride, palladium dichlorodiammine, ammonium chloropalladate, palladium dichlorotetraammine monohydrate, palladium (II) nitrate dihydrate, potassium chloropalladate, palladium (II) bis (acetylacetonate), and palladium acetate;
the lead-containing precursor is one or more of lead nitrate and lead acetate.
7. The preparation method according to claim 2, wherein the mixing in step B) is specifically:
mixing the carbon carrier obtained in the step A) with a palladium-containing precursor and a lead-containing precursor in a solution, performing ultrasonic treatment, and then violently stirring;
the ultrasonic time is more than 1 hour, and the vigorous stirring time is more than 24 hours.
8. The production method according to claim 2, wherein the hydrogen atmosphere includes hydrogen gas and either or both of argon gas and nitrogen gas;
the volume content of the hydrogen is 3-10%.
9. The preparation method according to claim 2, wherein the temperature of the high-temperature reduction is 500 to 750 ℃;
the high-temperature reduction time is 1-6 h;
the temperature rise speed of the high-temperature reduction is 1-20 ℃/min.
10. Small size Pd as set forth in claim 13Pb intermetallic compound, or the compound according to any one of claims 2 to 9Preparation method of small-size Pd3Pb intermetallic compound is used as catalyst for selective hydrogenation of alkyne.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010699630.8A CN111804291A (en) | 2020-07-20 | 2020-07-20 | Small-size Pd3Pb intermetallic compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010699630.8A CN111804291A (en) | 2020-07-20 | 2020-07-20 | Small-size Pd3Pb intermetallic compound and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111804291A true CN111804291A (en) | 2020-10-23 |
Family
ID=73455459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010699630.8A Pending CN111804291A (en) | 2020-07-20 | 2020-07-20 | Small-size Pd3Pb intermetallic compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111804291A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426460A (en) * | 2021-06-23 | 2021-09-24 | 中国科学技术大学 | The structure is carbon-loaded PdCu3Intermetallic compound and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55151533A (en) * | 1979-05-17 | 1980-11-26 | Asahi Chem Ind Co Ltd | Preparation of carboxylic acid ester |
| CN106466602A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
| CN110064423A (en) * | 2019-02-21 | 2019-07-30 | 中国科学技术大学 | Extra small multicomponent alloy composite material, preparation method and its application |
| CN110404573A (en) * | 2019-06-28 | 2019-11-05 | 中国科学技术大学 | A kind of preparation method and application of extra small palladium-base alloy material |
-
2020
- 2020-07-20 CN CN202010699630.8A patent/CN111804291A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55151533A (en) * | 1979-05-17 | 1980-11-26 | Asahi Chem Ind Co Ltd | Preparation of carboxylic acid ester |
| CN106466602A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| CN109174085A (en) * | 2018-09-06 | 2019-01-11 | 中国科学院金属研究所 | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application |
| CN110064423A (en) * | 2019-02-21 | 2019-07-30 | 中国科学技术大学 | Extra small multicomponent alloy composite material, preparation method and its application |
| CN110404573A (en) * | 2019-06-28 | 2019-11-05 | 中国科学技术大学 | A kind of preparation method and application of extra small palladium-base alloy material |
Non-Patent Citations (1)
| Title |
|---|
| JUNBO ZHANG ET AL.: "Concavity Tuning of Intermetallic Pd−Pb Nanocubes for Selective Semihydrogenation Catalysis", 《CHEMISTRY OF MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426460A (en) * | 2021-06-23 | 2021-09-24 | 中国科学技术大学 | The structure is carbon-loaded PdCu3Intermetallic compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106505216B (en) | Metal oxide-carbon nano-substance complex, catalyst, fuel cell electrode catalyst layer and these manufacturing methods | |
| KR102335322B1 (en) | A catalyst for ammonia decomposition and the method for producing the same through vacuum firing | |
| CN111224117A (en) | Pt alloy catalyst with nanowire structure and preparation method and application thereof | |
| CN110404573A (en) | A kind of preparation method and application of extra small palladium-base alloy material | |
| CN111974435B (en) | Preparation method and application of high-stability Cu/N-doped carbon nanosheet catalyst | |
| CN110947388B (en) | Graphene aerogel supported nickel catalyst and preparation method and application thereof | |
| Liu et al. | Bimetallic Ag–hollow Pt heterodimers via inside-out migration of Ag in core–shell Ag–Pt nanoparticles at elevated temperature | |
| CN112916009A (en) | Preparation method of biomass-derived porous carbon-limited-domain monoatomic metal composite material | |
| CN112938936B (en) | Metal atom loaded nanocomposite and preparation method thereof | |
| CN110639549A (en) | Universal method for preparing high-stability noble metal monatomic catalyst | |
| CN103038158B (en) | Thermochemistry water decomposition redox material and hydrogen production method | |
| Long et al. | Construction of trace silver modified core@ shell structured Pt-Ni nanoframe@ CeO 2 for semihydrogenation of phenylacetylene | |
| CN108658038B (en) | Based on LiAlH4Hydrogen storage material and method for producing the same | |
| Zhang et al. | Ir 3 Pb alloy nanodendrites with high performance for ethanol electrooxidation and their enhanced durability by alloying trace Au | |
| CN111804291A (en) | Small-size Pd3Pb intermetallic compound and preparation method and application thereof | |
| JP2010198885A (en) | Platinum ordered lattice catalyst for fuel cell, and its manufacturing method | |
| Zhou et al. | Low‐Temperature Carbon Monoxide Oxidation with Au–Cu Meatball‐Like Cages Prepared by Galvanic Replacement | |
| JP6023790B2 (en) | Precious metal catalysts for oxidative dehydrogenation with low metal loading | |
| CN114515578B (en) | Catalyst for preparing carbon nano tube and preparation method and application thereof | |
| CN113426460A (en) | The structure is carbon-loaded PdCu3Intermetallic compound and preparation method and application thereof | |
| CN111375410A (en) | Preparation method of graphite alkynyl catalyst | |
| CN117399014B (en) | Preparation method and application of finite field ammonia decomposition catalyst | |
| WO2024005062A1 (en) | Ammonia synthesis catalyst, method for manufacturing same, and method for synthesizing ammonia using said ammonia synthesis catalyst | |
| CN115318312B (en) | High-stability platinum-carbon catalyst and preparation method and application thereof | |
| CN117399040A (en) | Synthesis method of carbon-containing intermetallic compound nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201023 |