CN111437855B - Supported palladium-nickel bimetallic nano-alloy catalytic material and preparation method thereof - Google Patents
Supported palladium-nickel bimetallic nano-alloy catalytic material and preparation method thereof Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 34
- 239000000956 alloy Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000005291 magnetic effect Effects 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- 239000011259 mixed solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- 239000013310 covalent-organic framework Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 22
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 239000011258 core-shell material Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 9
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 20
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 20
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 12
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 10
- 239000004305 biphenyl Substances 0.000 description 10
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000005298 paramagnetic effect Effects 0.000 description 3
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/396—Distribution of the active metal ingredient
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- 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
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a supported palladium-nickel bimetallic nano-alloy catalytic material, wherein a carrier of the material is a yolk-eggshell type compound, an inner core of the carrier is magnetic nano-iron particles, an outer shell of the carrier is a nitrogen-doped carbon polyhedron obtained by crosslinking and carbonizing 4,4' -diaminobiphenyl and trihydroxy benzene, and an active load of the catalytic material is palladium-nickel bimetallic nano-alloy. The catalytic material has high catalytic reaction activity and stability, and has wide application prospect in the fields of biological pharmacy, chemical industry, automobile exhaust treatment, sewage treatment and the like.
Description
The technical field is as follows:
the invention relates to a supported palladium-nickel bimetallic nano-alloy catalytic material and a preparation method thereof, belonging to the field of heterogeneous catalytic materials.
Technical background:
the nano noble metal catalytic material shows high catalytic activity in reactions such as selective reduction of nitro compounds, CO oxidation and the like, and is widely concerned by people. Particularly, some cheap non-noble metals are added into noble metal nano particles to form the bimetallic nano alloy catalytic material, so that the catalytic activity of the catalytic material can be further improved, and the cost of the catalytic material is reduced.
The chinese patent with application number 201711377594.8 discloses a preparation method of a platinum-nickel alloy catalyst, which obtains the platinum-nickel alloy catalyst by reacting carbon-supported metal nickel nanoparticles with chloroplatinic acid. Chinese patent application No. 201610601513.7 discloses a preparation method of a carbon quantum dot/graphene-supported PtM alloy catalyst, wherein M is one of Fe, co, ni, cu, mn or Sn, and the catalytic material exhibits better catalytic performance and has better catalytic activity and economic value compared with the conventional single noble metal catalytic material. Therefore, the preparation and performance exploration of the noble metal-non-noble metal bimetal alloy catalytic material are subjects with important research significance. However, the above catalytic materials still have many problems such as small specific surface area, non-uniform pore channels, difficult recovery, low catalytic activity, and poor stability.
The invention content is as follows:
the technical problem is as follows: the invention aims to provide a supported palladium-nickel bimetallic nano-alloy catalytic material and a preparation method thereof.
The technical scheme is as follows:
a supported palladium-nickel bimetallic nano-alloy catalytic material is characterized in that a carrier of the catalytic material is a yolk-eggshell type compound, wherein the inner core of the carrier is magnetic nano-iron particles, the shell of the carrier is a nitrogen-doped carbon polyhedron, and an active load is palladium-nickel bimetallic nano-alloy particles.
The nitrogen-doped carbon polyhedron is obtained by high-temperature carbonization of a covalent organic framework polymer formed by crosslinking 4,4' -diaminobiphenyl and trihydroxy benzene. The size of the magnetic nano iron particles is 10-50 nm, the thickness of the nitrogen-doped carbon polyhedron is 30-100 nm, and the size of the palladium-nickel bimetallic nano alloy particles is 1-10 nm.
The specific preparation method of the catalytic material comprises the following steps:
a) Preparing 0.2-0.8 wt% of ferric chloride aqueous solution at room temperature, adding 0.002-0.01 wt% of potassium dihydrogen phosphate aqueous solution according to the mass ratio of 0.005: 1-0.05: 1 of potassium dihydrogen phosphate to ferric chloride, stirring for reaction for 30-60 min, transferring to a reaction kettle, reacting for 36-72 h at 80-120 ℃, centrifugally separating, washing precipitate with 100-500 times of deionized water of the mass of ferric chloride, and vacuum drying for 8-12 h at 70-100 ℃ to obtain Fe 2 O 3 A nanoparticle;
b) Preparing a hydrochloric acid solution with the mass fraction of 0.1-0.4 wt% at room temperature, adding 4,4 '-diaminobiphenyl according to the mass ratio of 0.001: 1-0.004: 1 of 4,4' -diaminobiphenyl and a hydrochloric acid solution, adding a sodium nitrite solution with the mass fraction of 0.5-1.0 wt% according to the mass ratio of 0.2: 1-0.4: 1 of a sodium nitrite solution and a hydrochloric acid solution, uniformly mixing and stirring at 0-4 ℃, and adjusting the pH of the mixed solution to 6-8 by using an inorganic alkaline water solution with the mass fraction of 10-50 wt% to obtain an aminobiphenyl mixed solution;
c) Preparing 0.5-5 wt% sodium carbonate aqueous solution at room temperature according to Fe 2 O 3 The mass ratio of the nano particles to the sodium carbonate is 0.2: 1-1: 1, and the Fe prepared in the step a) is added 2 O 3 Nanoparticles of trihydroxybenzene and Fe 2 O 3 Of nanoparticlesAdding trihydroxy benzene into the mixture according to the mass ratio of 0.2: 1-1: 1, mixing and stirring the mixture for 30-60 min at the temperature of 0-4 ℃ to obtain trihydroxy benzene mixed solution, adding the aminobiphenyl mixed solution prepared in the step b) into the trihydroxy benzene mixed solution according to the mass ratio of 1: 1-5: 1 of the aminobiphenyl mixed solution and the trihydroxy benzene mixed solution, stirring and reacting the mixture for 10-15 h at the temperature of 0-4 ℃, performing centrifugal separation, and sequentially using 100-500 times of Fe 2 O 3 Washing and precipitating with deionized water and ethanol with the mass of nano particles, and drying in vacuum for 10-12 h at the temperature of 60-80 ℃ to obtain Fe 2 O 3 -a covalent organic framework polymer core-shell complex;
d) According to Fe 2 O 3 The mass ratio of the covalent organic framework polymer core-shell compound to the deionized water is 0.01: 1-0.1: 1, and the Fe prepared in the step c) is added 2 O 3 -covalent organic framework polymer core-shell complexes dispersed in deionized water as palladium source with Fe 2 O 3 The mass ratio of the covalent organic frame polymer core-shell compound is 0.01: 1-0.1: 1, a palladium source is added, the nickel source is added according to the mass ratio of 0.2: 1-2: 1, the ultrasonic dispersion is carried out for 30-60 min, the pH value of the solution is adjusted to 10-14 by using 0.1-1 wt% of sodium hydroxide aqueous solution, the stirring reaction is carried out for 2-8 h, the centrifugal separation is carried out, and 50-500 times of Fe is used for precipitation 2 O 3 Washing the covalent organic framework polymer core-shell composite with deionized water, and vacuum drying at 60-80 ℃ for 8-12 h to obtain Fe 2 O 3 -a covalent organic framework polymer/Pd-Ni alloy composite;
e) Subjecting the Fe obtained in step d) 2 O 3 Placing the covalent organic framework polymer/Pd-Ni alloy composite material in a tubular furnace, introducing reducing gas, adjusting the gas flow to 0.2-3 mL/min, reducing for 2-6 h at 600-800 ℃, and cooling to room temperature to obtain the supported palladium-nickel bimetallic nano alloy catalytic material.
The preparation method of the supported palladium-nickel bimetallic nano-alloy catalytic material is characterized in that the inorganic base in the step b) is one of sodium hydroxide, sodium carbonate and sodium bicarbonate. The palladium source in the step d) is one of palladium chloride and palladium acetate, and the nickel source is one of nickel nitrate, nickel acetate and nickel chloride. The reducing gas in the step e) is hydrogen-helium mixed gas with the volume ratio of 1: 5-1: 10. The invention has the characteristics that:
(1) The catalytic material carrier is a yolk-eggshell type compound, and the nitrogen-doped carbon polyhedron of the shell of the carrier has a higher specific surface area, so that the adsorption effect of the catalyst on a reaction medium can be promoted; the magnetic iron particles in the carrier core have stronger magnetic response characteristics, and can be convenient for the recovery of the catalyst in liquid phase reaction.
(2) The active load of the catalytic material is palladium-nickel bimetallic nano-alloy particles, and the introduction of nickel can improve the chemical environment of the palladium particles, improve the catalytic activity of the catalyst and reduce the cost of the catalyst.
(3) Covalent organic framework polymer formed by crosslinking 4,4' -diaminobiphenyl and trihydroxybenzene is used as a sacrificial template, and palladium-nickel alloy nanoparticles can be directionally anchored, so that the dispersibility of an active load on catalysis is improved.
The specific embodiment is as follows:
example 1:
1. preparation of the catalytic material:
dissolving 0.2g of ferric chloride in 99.8g of deionized water at 25 ℃ to prepare a ferric chloride aqueous solution with the mass fraction of 0.2%; adding 150g of potassium dihydrogen phosphate aqueous solution with the mass fraction of 0.004%, stirring for reaction for 45min, transferring to a reaction kettle, reacting for 48h at 120 ℃, centrifugally separating, washing the precipitate with 20g of deionized water, and drying in vacuum at 100 ℃ for 12h to obtain Fe 2 O 3 A nanoparticle;
preparing 37g of hydrochloric acid solution with the mass fraction of 0.1% at 25 ℃, and then adding 111mg of 4,4' -diaminobiphenyl; adding 12.95g of sodium nitrite aqueous solution with the mass fraction of 1.0%, uniformly stirring at 1 ℃, and adjusting the pH of the mixed solution to 7.5 by using sodium bicarbonate solution with the mass fraction of 10% to obtain aminobiphenyl mixed solution;
preparing 25g of sodium carbonate aqueous solution with the mass fraction of 4.0% at 25 ℃; 1g of Fe was additionally added 2 O 3 Adding 1g of trihydroxy benzene into the nanoparticles, and stirring the solution at 1 deg.C for 60min to obtain a homogeneous solutionTrihydroxy benzene mixed solution, 10g of aminobiphenyl mixed solution is added into 5g of trihydroxy benzene mixed solution, stirring and reacting are carried out for 10h at the temperature of 3 ℃, centrifugal separation is carried out, sediment is washed by 100g of deionized water and ethanol respectively, vacuum drying is carried out for 10h at the temperature of 75 ℃, and Fe is obtained 2 O 3 -a covalent organic framework core-shell complex;
0.5g of the obtained Fe was taken 2 O 3 -covalent organic framework core-shell complexes dispersed in 10g of deionized water. Then 0.7mL of palladium chloride solution with the concentration of 50mg/mL and 1.4mL of nickel chloride solution with the concentration of 50mg/mL are added, and ultrasonic dispersion is carried out for 30min. Preparing 0.3 mass percent sodium hydroxide solution, adjusting the pH of the mixed solution to 10, stirring for reaction for 8 hours, centrifugally separating, washing the precipitate with 25g of deionized water, and drying in vacuum at 80 ℃ for 8 hours to obtain Fe 2 O 3 -a covalent organic framework/Pd-Ni alloy composite;
the obtained Fe 2 O 3 Putting the covalent organic framework/Pd-Ni alloy composite material into a tubular furnace, introducing hydrogen-helium mixed gas with the volume ratio of 1: 9, adjusting the gas flow to be 0.8mL/min, reducing at 800 ℃ for 4h, and cooling to room temperature to obtain the supported palladium-nickel bimetallic nano alloy catalytic composite material.
2. The structural and performance characteristics of the catalytic material:
the transmission electron microscope tests show that the magnetic nano iron particle size of the catalytic material is 10nm, the nitrogen-doped carbon polyhedron is 50nm, and the palladium-nickel bimetallic nano alloy particle size is 1nm. The material has super-paramagnetic performance, and the saturation magnetization of the material is 166emu/g.
3. Evaluation of catalytic Performance of the catalytic Material:
the method takes the biphenyl generated by catalyzing phenylboronic acid and iodobenzene as a probe. Preparing 15mL of ethanol-DMF solution with the volume ratio of 2: 1, sequentially adding 6mmol of phenylboronic acid, 5mmol of iodobenzene, 5mmol of sodium carbonate and 0.25g of catalytic material, and reacting for 1 hour by microwave until the conversion rate of biphenyl is 97%. Meanwhile, after the catalytic material is continuously recycled for 5 times, the conversion rate can be maintained to be more than 93%.
Example 2:
1. preparation of catalytic material:
at 25 deg.C, 0.3g of ferric chlorideDissolving the mixture in 99.7g of deionized water to prepare a ferric chloride aqueous solution with the mass fraction of 0.3%; adding 120g of monopotassium phosphate aqueous solution with the mass fraction of 0.010 percent, stirring for reaction for 40min, transferring the mixture into a reaction kettle, reacting for 72h at the temperature of 110 ℃, centrifugally separating, washing the precipitate with 150g of deionized water, and drying for 10h at the temperature of 70 ℃ in vacuum to obtain Fe 2 O 3 A nanoparticle;
preparing 18.5g of hydrochloric acid solution with the mass fraction of 0.2% at the temperature of 25 ℃, and then adding 37mg4,4' -diaminobiphenyl; adding 3.7g of sodium nitrite aqueous solution with the mass fraction of 0.7%, uniformly stirring at 2 ℃, and adjusting the pH of the mixed solution to 7 by using sodium hydroxide solution with the mass fraction of 30% to obtain aminobiphenyl mixed solution;
preparing 100g of sodium carbonate aqueous solution with the mass fraction of 0.5% at 25 ℃; 0.1g of Fe was additionally added 2 O 3 Adding 0.06g of trihydroxy benzene into nanoparticles, stirring the solution at 2 ℃ for 30min to obtain trihydroxy benzene mixed solution, adding 10g of aminobiphenyl mixed solution into 10g of trihydroxy benzene mixed solution, stirring at 4 ℃ for 15h, performing centrifugal separation, washing precipitates with 30g of deionized water and ethanol respectively, and performing vacuum drying at 80 ℃ for 12h to obtain Fe 2 O 3 -a covalent organic framework core-shell complex;
0.5g of the obtained Fe was taken 2 O 3 -covalent organic framework core-shell complexes dispersed in 5g of deionized water. Then 0.1mL of palladium acetate solution with the concentration of 50mg/mL and 1.5mL of nickel nitrate solution with the concentration of 50mg/mL are added, and ultrasonic dispersion is carried out for 60min. Preparing 0.7 mass percent sodium hydroxide solution, adjusting the pH of the mixed solution to 12, stirring for reaction for 5 hours, centrifugally separating, washing the precipitate with 200g of deionized water, and drying in vacuum at 70 ℃ for 8 hours to obtain Fe 2 O 3 -a covalent organic framework/Pd-Ni alloy composite;
the obtained Fe 2 O 3 Putting the covalent organic framework/Pd-Ni alloy composite material into a tubular furnace, introducing hydrogen-helium mixed gas with the volume ratio of 1: 5, adjusting the gas flow to be 2.0mL/min, reducing at 750 ℃ for 2h, and cooling to room temperature to obtain the supported palladium-nickel bimetallic nano alloy catalytic composite material.
2. The structural and performance characteristics of the catalytic material:
the transmission electron microscope tests show that the magnetic nano-iron particle size of the catalytic material is 15nm, the nitrogen-doped carbon polyhedron thickness is 65nm, and the palladium-nickel bimetallic nano-alloy particle size is 3nm. The material has super paramagnetic performance, and the saturation magnetization of the material is 176emu/g.
3. Evaluation of catalytic Properties of the catalytic Material:
the method takes the biphenyl generated by catalyzing phenylboronic acid and iodobenzene as a probe. Preparing 15mL of ethanol-DMF solution with the volume ratio of 2: 1, sequentially adding 6mmol of phenylboronic acid, 5mmol of iodobenzene, 5mmol of sodium carbonate and 0.25g of catalytic material, and reacting for 1 hour by microwave until the conversion rate of biphenyl is 97%. Meanwhile, after the catalytic material is continuously recycled for 6 times, the conversion rate can be maintained to be more than 93%.
Example 3:
1. preparation of catalytic material:
dissolving 0.5g of ferric chloride in 99.5g of deionized water at 25 ℃ to prepare a ferric chloride aqueous solution with the mass fraction of 0.5%; adding 93.75g of monopotassium phosphate aqueous solution with the mass fraction of 0.008 percent, stirring for reaction for 30min, transferring the mixture into a reaction kettle, reacting for 54h at 90 ℃, centrifugally separating, washing the precipitate with 200g of deionized water, and drying for 9h at 80 ℃ in vacuum to obtain Fe 2 O 3 A nanoparticle;
preparing 18.5g of hydrochloric acid solution with the mass fraction of 0.2% at the temperature of 25 ℃, and then adding 74mg of 4,4' -diaminobiphenyl; adding 7.4g of 0.9 mass percent sodium nitrite aqueous solution, uniformly stirring at 4 ℃, and adjusting the pH of the mixed solution to 8 by using 20 mass percent sodium carbonate solution to obtain aminobiphenyl mixed solution;
preparing 100g of sodium carbonate aqueous solution with the mass fraction of 1.5% at 25 ℃; 0.6g of Fe was additionally added 2 O 3 Adding 0.12g of trihydroxy benzene into nanoparticles, stirring the solution at 0 ℃ for 45min to obtain trihydroxy benzene mixed solution, adding 10g of aminobiphenyl mixed solution into 2g of trihydroxy benzene mixed solution, stirring at 1 ℃ for 10h, centrifuging, washing the precipitate with 240g of deionized water and ethanol respectively, and vacuum drying at 70 ℃ for 10h to obtain Fe 2 O 3 -covalent organic frameworksA core-shell composite;
0.5g of the obtained Fe was taken 2 O 3 -covalent organic framework core-shell complexes dispersed in 50g of deionized water. Then 1.0mL of palladium chloride solution with the concentration of 50mg/mL and 1.0mL of nickel acetate solution with the concentration of 50mg/mL are added, and ultrasonic dispersion is carried out for 40min. Preparing 0.5 mass percent sodium hydroxide solution, adjusting the pH of the mixed solution to 14, stirring for reaction for 3.5 hours, centrifugally separating, washing the precipitate with 50g of deionized water, and vacuum-drying at 60 ℃ for 12 hours to obtain Fe 2 O 3 -a covalent organic framework/Pd-Ni alloy composite;
the obtained Fe 2 O 3 Putting the covalent organic framework/Pd-Ni alloy composite material into a tubular furnace, introducing hydrogen-helium mixed gas with the volume ratio of 1: 7.5, adjusting the gas flow to be 1.5mL/min, reducing at 650 ℃ for 5h, and cooling to room temperature to obtain the supported palladium-nickel bimetallic nano alloy catalytic composite material.
2. The structural and performance characteristics of the catalytic material:
the magnetic nano iron particle size of the catalytic material is 17nm, the nitrogen-doped carbon polyhedron thickness is 73nm, and the palladium-nickel bimetallic nano alloy particle cluster size is 3nm through a transmission electron microscope test. The material has super paramagnetic performance, and the saturation magnetization of the material is 172emu/g.
3. Evaluation of catalytic Performance of the catalytic Material:
the method takes the biphenyl generated by catalyzing phenylboronic acid and iodobenzene as a probe. Preparing 15mL of ethanol-DMF solution with the volume ratio of 2: 1, sequentially adding 6mmol of phenylboronic acid, 5mmol of iodobenzene, 5mmol of sodium carbonate and 0.25g of catalytic material, and carrying out microwave reaction for 1 hour until the conversion rate of biphenyl is 98%. Meanwhile, after the catalytic material is continuously recycled for 5 times, the conversion rate can be maintained to be more than 93%.
Example 4:
1. preparation of the catalytic material:
dissolving 0.6g of ferric chloride in 99.4g of deionized water at 25 ℃ to prepare a ferric chloride aqueous solution with the mass fraction of 0.6%; adding 500g of 0.006% potassium dihydrogen phosphate water solution, stirring for 50min, transferring into a reaction kettle, reacting at 100 deg.C for 36 hr, centrifuging, precipitating with 120g of deionized waterWashing with water, vacuum drying at 90 deg.C for 8h to obtain Fe 2 O 3 A nanoparticle;
preparing 14.8g of hydrochloric acid solution with the mass fraction of 0.25% at 25 ℃, and then adding 14.8mg of 4,4' -diaminobiphenyl; adding 3.7g of sodium nitrite aqueous solution with the mass fraction of 0.6%, uniformly mixing and stirring at 3 ℃, and adjusting the pH of the mixed solution to 6.5 by using sodium carbonate solution with the mass fraction of 40% to obtain aminobiphenyl mixed solution;
preparing 100g of sodium carbonate aqueous solution with the mass fraction of 5% at 25 ℃; 3g of Fe was additionally added 2 O 3 Adding 2.4g of trihydroxy benzene into nanoparticles, stirring the solution at 3 ℃ for 40min to react to obtain trihydroxy benzene mixed solution, adding 10g of aminobiphenyl mixed solution into 2.5g of trihydroxy benzene mixed solution, stirring at 0 ℃ for 15h, performing centrifugal separation, washing precipitates with 600g of deionized water and ethanol respectively, and performing vacuum drying at 60 ℃ for 12h to obtain Fe 2 O 3 -a covalent organic framework core-shell complex;
0.7g of the obtained Fe was taken 2 O 3 -covalent organic framework core-shell complexes dispersed in 10g of deionized water. Then 0.42mL of palladium chloride solution with the concentration of 50mg/mL and 2.1mL of nickel nitrate solution with the concentration of 50mg/mL are added, and ultrasonic dispersion is carried out for 45min. Preparing 0.1 mass percent sodium hydroxide solution, adjusting the pH of the mixed solution to 11, stirring for reaction for 6.5 hours, centrifugally separating, washing the precipitate with 350g of deionized water, and drying in vacuum at 80 ℃ for 10 hours to obtain Fe 2 O 3 -a covalent organic framework/Pd-Ni alloy composite;
the obtained Fe 2 O 3 Putting the covalent organic framework/Pd-Ni alloy composite material into a tubular furnace, introducing hydrogen-helium mixed gas with the volume ratio of 1: 10, adjusting the gas flow to be 0.2mL/min, reducing for 6h at 600 ℃, and cooling to room temperature to obtain the supported palladium-nickel bimetallic nano alloy catalytic composite material.
2. The structural and performance characteristics of the catalytic material:
the magnetic nano iron particle size of the catalytic material is 17nm, the nitrogen-doped carbon polyhedron thickness is 79nm, and the palladium-nickel bimetallic nano alloy particle size is 1nm through a transmission electron microscope test. The material has super paramagnetic performance, and the saturation magnetization of the material is 169emu/g.
3. Evaluation of catalytic Performance of the catalytic Material:
the method takes biphenyl generated by catalyzing phenylboronic acid and iodobenzene as a probe. 15mL of ethanol-DMF solution with the volume ratio of 2: 1 is prepared, 6mmol of phenylboronic acid, 5mmol of iodobenzene, 5mmol of sodium carbonate and 0.25g of catalytic material are sequentially added, and the conversion rate of biphenyl is 98% after 1 h. Meanwhile, after the catalytic material is continuously recycled for 6 times, the conversion rate can be maintained to be more than 93%.
Example 5:
1. preparation of catalytic material:
dissolving 0.8g of ferric chloride in 99.2g of deionized water at 25 ℃ to prepare a ferric chloride aqueous solution with the mass fraction of 0.8%; adding 200g of potassium dihydrogen phosphate aqueous solution with the mass fraction of 0.002%, stirring for reaction for 60min, transferring to a reaction kettle, reacting for 80h at 80 ℃, centrifugally separating, washing precipitate with 240g of deionized water, and vacuum drying at 85 ℃ for 11h to obtain Fe 2 O 3 A nanoparticle;
preparing 9.25g of hydrochloric acid solution with the mass fraction of 0.4% at 25 ℃, and then adding 23mg of 4,4' -diaminobiphenyl; adding 2.775g of sodium nitrite aqueous solution with the mass fraction of 0.5%, uniformly stirring at 0 ℃, and adjusting the pH of the mixed solution to 6 by using sodium bicarbonate solution with the mass fraction of 50% to obtain aminobiphenyl mixed solution;
preparing 100g of sodium carbonate aqueous solution with the mass fraction of 3% at 25 ℃; 2.4g of Fe was additionally added 2 O 3 Adding 0.96g of trihydroxy benzene into nanoparticles, stirring the solution at 4 ℃ for 50min to obtain trihydroxy benzene mixed solution, adding 9g of aminobiphenyl mixed solution into 3g of trihydroxy benzene mixed solution, stirring at 2 ℃ for 12h, performing centrifugal separation, washing precipitates with 1200g of deionized water and ethanol respectively, and performing vacuum drying at 60 ℃ for 11h to obtain Fe 2 O 3 -a covalent organic framework core-shell complex;
0.6g of the obtained Fe was taken 2 O 3 -covalent organic framework core-shell complexes dispersed in 20g of deionized water. Then 0.6mL of palladium acetate solution with the concentration of 50mg/mL and 1mL of nickel acetate solution with the concentration of 50mg/mL are addedAnd carrying out ultrasonic dispersion for 50min. Preparing 1% sodium hydroxide solution by mass fraction, adjusting the pH of the mixed solution to 13, stirring for reaction for 2h, centrifugally separating, washing precipitate with 120g deionized water, and vacuum drying at 60 ℃ for 12h to obtain Fe 2 O 3 -a covalent organic framework/Pd-Ni alloy composite;
the obtained Fe 2 O 3 Putting the covalent organic framework/Pd-Ni alloy composite material into a tubular furnace, introducing hydrogen-helium mixed gas with the volume ratio of 1: 6, adjusting the gas flow to be 3.0mL/min, reducing for 3h at 700 ℃, and cooling to room temperature to obtain the supported palladium-nickel bimetal nano alloy catalytic composite material.
2. The structural and performance characteristics of the catalytic material:
the magnetic nano iron particle size of the catalytic material is 20nm, the nitrogen-doped carbon polyhedron thickness is 80nm, and the palladium-nickel bimetallic nano alloy particle size is 3nm through a transmission electron microscope test. The material has super-paramagnetic performance, and the saturation magnetization of the material is 175emu/g.
3. Evaluation of catalytic Properties of the catalytic Material:
the method takes the biphenyl generated by catalyzing phenylboronic acid and iodobenzene as a probe. 15mL of ethanol-DMF solution with the volume ratio of 2: 1 is prepared, 6mmol of phenylboronic acid, 5mmol of iodobenzene, 5mmol of sodium carbonate and 0.25g of catalytic material are sequentially added, and the conversion rate of biphenyl is 98% after 1 h. Meanwhile, after the catalytic material is continuously recycled for 6 times, the conversion rate can be maintained to be more than 93%.
Claims (6)
1. A supported palladium-nickel bimetallic nano-alloy catalytic material is characterized in that a carrier of the catalytic material is a yolk-eggshell type compound, wherein the inner core of the carrier is magnetic nano-iron particles, the shell of the carrier is a nitrogen-doped carbon polyhedron, a covalent organic framework polymer formed by crosslinking 4,4' -diaminobiphenyl and trihydroxy benzene is carbonized at high temperature to obtain the supported palladium-nickel bimetallic nano-alloy particles.
2. The supported palladium-nickel bimetallic nano-alloy catalytic material as claimed in claim 1, wherein the size of the magnetic nano-iron particles is 10-50 nm, the thickness of the nitrogen-doped carbon polyhedron is 30-100 nm, and the size of the palladium-nickel bimetallic nano-alloy particles is 1-10 nm.
3. A method for preparing a supported palladium-nickel bimetallic nano-alloy catalytic material as in any one of claims 1-2, comprising the following steps:
a) Preparing 0.2-0.8 mass percent of iron chloride aqueous solution at room temperature, adding 0.002-0.01 mass percent of potassium dihydrogen phosphate aqueous solution according to the mass ratio of the potassium dihydrogen phosphate to the iron chloride of 0.005: 1-0.05: 1, stirring and reacting for 30-60 min, transferring the mixture into a reaction kettle, reacting for 36-72 h at the temperature of 80-120 ℃, centrifugally separating, washing the precipitate by using deionized water with the mass of 100-500 times that of the iron chloride, and drying for 8-12 h at the temperature of 70-100 ℃ in vacuum to obtain Fe 2 O 3 A nanoparticle;
b) Preparing a hydrochloric acid solution with the mass fraction of 0.1-0.4% at room temperature, adding 4,4 '-diaminobiphenyl according to the mass ratio of 0.001: 1-0.004: 1 of 4,4' -diaminobiphenyl to the hydrochloric acid solution, adding a sodium nitrite solution with the mass fraction of 0.5-1.0% according to the mass ratio of 0.2: 1-0.4: 1 of the sodium nitrite solution to the hydrochloric acid solution, uniformly mixing and stirring at 0-4 ℃, and adjusting the pH of the mixed solution to 6-8 by using an inorganic alkaline substance aqueous solution with the mass fraction of 10-50% to obtain an aminobiphenyl mixed solution;
c) Preparing 0.5-5% sodium carbonate aqueous solution at room temperature according to the weight percentage of Fe 2 O 3 The mass ratio of the nano particles to the sodium carbonate is 0.2: 1-1: 1, and the Fe prepared in the step a) is added 2 O 3 Nanoparticles of trihydroxybenzene and Fe 2 O 3 Adding trihydroxy benzene into the nano particles according to the mass ratio of 0.2: 1-1: 1, mixing and stirring the trihydroxy benzene at the temperature of 0-4 ℃ for 30-60 min to obtain trihydroxy benzene mixed solution, adding the aminobiphenyl mixed solution prepared in the step b) into the trihydroxy benzene mixed solution according to the mass ratio of 1: 1-5: 1 of aminobiphenyl mixed solution and trihydroxy benzene mixed solution, stirring and reacting the aminobiphenyl mixed solution at the temperature of 0-4 ℃ for 10-15 h, performing centrifugal separation, and sequentially using 100-500 times of Fe 2 O 3 Nanoparticle materialWashing the precipitate with deionized water and ethanol, and vacuum drying at 60-80 deg.c for 10-12 hr to obtain Fe 2 O 3 -a covalent organic framework polymer core-shell complex;
d) According to Fe 2 O 3 The mass ratio of the covalent organic framework polymer core-shell compound to the deionized water is 0.01: 1-0.1: 1, and the Fe prepared in the step c) is added 2 O 3 -covalent organic framework polymer core-shell complexes dispersed in deionized water as palladium source with Fe 2 O 3 The mass ratio of the covalent organic framework polymer core-shell compound is 0.01: 1-0.1: 1, a palladium source is added, the nickel source is added according to the mass ratio of the nickel source to the palladium source of 0.2: 1-2: 1, ultrasonic dispersion is carried out for 30-60 min, the pH value of the solution is adjusted to 10-14 by using a sodium hydroxide aqueous solution with the mass fraction of 0.1-1%, stirring reaction is carried out for 2-8 h, centrifugal separation is carried out, and 50-500 times of Fe is used for precipitation 2 O 3 Washing the covalent organic framework polymer core-shell composite with deionized water, and vacuum drying at 60-80 ℃ for 8-12 h to obtain Fe 2 O 3 -a covalent organic framework polymer/Pd-Ni alloy composite;
e) Subjecting the Fe obtained in step d) 2 O 3 Putting the covalent organic framework polymer/Pd-Ni alloy composite material in a tubular furnace, introducing reducing gas, adjusting the gas flow to 0.2-3 mL/min, reducing at 600-800 ℃ for 2-6 h, and cooling to room temperature to obtain the supported palladium-nickel bimetal nano alloy catalytic material.
4. The method for preparing a supported palladium-nickel bimetallic nano-alloy catalytic material as claimed in claim 3, wherein the inorganic alkaline substance in step b) is one of sodium hydroxide, sodium carbonate and sodium bicarbonate.
5. The method for preparing a supported palladium-nickel bimetallic nano-alloy catalytic material as claimed in claim 3, wherein the palladium source in step d) is one of palladium chloride and palladium acetate, and the nickel source is one of nickel nitrate, nickel acetate and nickel chloride.
6. The method for preparing a supported palladium-nickel bimetallic nano-alloy catalytic material as claimed in claim 3, wherein the reducing gas in step e) is a hydrogen-helium mixed gas with a volume ratio of 1: 5-1: 10.
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