CN111250108A - Supported palladium multilevel structure catalytic material and preparation method and application thereof - Google Patents
Supported palladium multilevel structure catalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111250108A CN111250108A CN202010249291.3A CN202010249291A CN111250108A CN 111250108 A CN111250108 A CN 111250108A CN 202010249291 A CN202010249291 A CN 202010249291A CN 111250108 A CN111250108 A CN 111250108A
- Authority
- CN
- China
- Prior art keywords
- nano
- catalytic material
- supported palladium
- deionized water
- taking
- 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.)
- Withdrawn
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 16
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 239000002071 nanotube Substances 0.000 claims abstract description 14
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000002135 nanosheet Substances 0.000 claims description 17
- 239000002070 nanowire Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000005750 Copper hydroxide Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 6
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000006056 electrooxidation reaction Methods 0.000 claims description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 17
- 238000012512 characterization method Methods 0.000 description 13
- 238000006069 Suzuki reaction reaction Methods 0.000 description 9
- 239000004305 biphenyl Chemical class 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- -1 biaryl compounds Chemical class 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000012691 Cu precursor Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940008309 acetone / ethanol Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910001868 water Inorganic materials 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention providesThe invention provides a supported palladium multilevel structure catalytic material, a preparation method and application thereof. Then stably loading palladium nano-particles on a three-dimensional multistage nanotube array by utilizing an in-situ redox reaction, wherein the catalytic material is represented as Pd/Co (OH)2/Cu(OH)2The catalytic material shows higher catalytic activity to Suzuki-Miyaura reaction under mild reaction conditions and has good cycle stability. The catalyst has the advantages of simple preparation, easy separation and recovery, high catalytic activity, low cost and the like, and has good application prospect.
Description
The technical field is as follows:
the invention relates to a catalytic material for catalytic coupling reaction and preparation thereof, in particular to a supported palladium multilevel structure catalytic material, preparation thereof and application thereof in catalyzing Suzuki reactions.
Background art:
the coupling reaction is considered to be one of the most convenient methods for producing biaryl compounds and substituted arene compounds in the field of organic synthesis at present, and can be widely applied to synthesis of various natural products and organic materials. Suzuki-Miyaura reaction (Suzuki-Miyaura reaction) is a novel and typical coupling reaction, can be used for synthesizing derivatives of polyene hydrocarbon, styrene and biphenyl, and has the advantages of mild reaction conditions, easiness in operation, stronger substrate adaptability and functional group tolerance, easiness in separation and treatment of raw materials and byproducts, and the like.
At present, the use of homogeneous Pd-based catalysts is the most common catalytic mode of operation for suzuki reactions. However, the conventional homogeneous catalyst Pd has low utilization rate and is difficult to recover, which not only causes increase in cost, but also greatly limits its application in pharmaceutical industry. Therefore, supported heterogeneous Pd-based catalysts would be one of the most promising alternatives to solve the above problems at present. For supported catalysts, the small particle size and highly dispersed state of the supported nanoparticles generally favor enhanced catalytic activity. According to the current research, most of supported Pd-based catalyst materials such as hollow three-dimensional multilevel nano-materials [ Energy environ. sci.2015,8(3): 702-.
In the previous work, we successfully designed and prepared a hollow tubular iron oxide/copper base electrode material (chinese patent 201810000630.7), wherein the hollow tubular structure makes it have large specific surface area, multiple mass transfer channels and good structural stability, so we imagine that, using similar experimental ideas, we firstly prepared a three-dimensional multilevel cobalt hydroxide/copper hydroxide/foam copper base material with a hollow tubular structure, and then utilized a simple in-situ redox reaction to stably and highly dispersedly load Pd nanoparticles on a three-dimensional multilevel nanotube array, and finally realized the rapid and efficient preparation of a supported palladium multilevel structure catalytic material. Thanks to the multi-stage structure and the uniformly dispersed ultra-small particle size Pd nanoparticles, the structured catalyst exhibits excellent catalytic activity for coupling reaction under mild reaction conditions and has good cycle stability. The catalyst has the advantages of convenient separation and recovery, high catalytic activity, simple synthesis, low cost and the like, so that the catalyst is hopeful to become an industrialized product with prospect. It is expected that this method can be used for synthesizing other supported nano-catalysts with multi-stage structures and applied to different heterogeneous catalysis fields.
The invention content is as follows:
the invention aims to provide a supported palladium multilevel structure catalytic material and a preparation method thereof.
The supported palladium multilevel structure catalytic material is expressed as Pd/Co (OH)2/Cu(OH)2/CF, where CF is a foamed copper substrate, Cu (OH)2For growing nanotubes with hollow structure on CF substrates, Co (OH)2For growth in Cu (OH)2Outer wall of nanotubePd is highly dispersed in Co (OH)2Nanoparticles on the surface of the nanosheets; the whole body is a supported palladium multilevel structure catalytic material.
The preparation method of the supported palladium multilevel structure catalytic material comprises the following steps: adopting alkaline oxidation etching, constant potential electrodeposition and in-situ redox method, firstly growing Cu (OH) on the surface of the foam copper substrate in situ2Array of nanowires, then electrodeposition in solution containing cobalt nitrate by potentiostatic potential, in Cu (OH)2Growing Co (OH) on the nanowire array2Nanosheets, resulting in Cu (OH) having a hollow structure2A nanotube; finally, the Pd nanoparticles are subjected to in-situ redox reaction in a sodium tetrachloropalladate solution to ensure that the Pd nanoparticles are distributed in Co (OH) in a highly dispersed manner2And (3) nanosheet surface, thereby obtaining the Pd-loaded three-dimensional nano array structure material. The material has good catalytic performance, has the advantages of easy separation and recovery, and can be applied to catalysis of coupling reaction.
The preparation method of the supported palladium multilevel structure catalytic material comprises the following specific steps:
A. ultrasonically cleaning the foamy copper by acetone, ethanol, hydrochloric acid and deionized water for 3-10min respectively, soaking the cleaned foamy copper in a mixed solution of ammonium persulfate with the concentration of 0.05-0.5mol/L and sodium hydroxide with the concentration of 1-5mol/L for 10-40min, cleaning by deionized water, and drying in an oven at the temperature of 60-70 ℃ to obtain copper hydroxide/foamy copper, which is expressed as Cu (OH)2(ii)/CF; wherein Cu (OH)2Is a nanowire array structure.
B. The Cu (OH) obtained in the step A2taking/CF as a working electrode, taking a Pt net or Pt wire electrode as a counter electrode, taking Ag/AgCl as a reference electrode, taking 0.1-0.50 mol/L cobalt nitrate solution as electrolyte, electrodepositing for 100-500 seconds under the condition that the constant potential is-0.5-1.0V, cleaning with deionized water, and drying in an oven at the temperature of 60-70 ℃ to obtain Co (OH)2/Cu(OH)2(ii)/CF; wherein Co (OH)2Is of a nano-sheet structure; due to electrochemical corrosion, Cu (OH)2The structure of (1) is changed from a nano wire into a hollow nano tube.
C. Subjecting the product obtained in step B toCo (OH)2/Cu(OH)2placing/CF in 0.002-0.02 mol/L tetrachloropalladate solution to soak for 10-60 min, washing with deionized water, and drying at room temperature to obtain Pd/Co (OH)2/Cu(OH)2and/CF. Wherein Pd is nano-particles with the particle size of 1-5 nm, and is distributed in Co (OH) in a highly dispersed way2And (3) the surface of the nanosheet.
The invention is characterized in that: cu (OH) in the electrodeposition process due to electrochemical corrosion2The nanowires are directionally dissolved to generate Cu (OH) with a hollow structure2A nanotube; when the in-situ redox reaction is carried out in the sodium tetrachloropalladate solution, Co (OH) can be utilized2The reducibility of the Pd nano-particles enables the Pd nano-particles to be rapidly and highly dispersed and distributed in Co (OH)2And (3) nanosheet surface, thereby obtaining the Pd-loaded three-dimensional nano array structure material.
Characterization and application test
FIG. 1 shows Co (OH) obtained in step B of example 12/Cu(OH)2Scanning Electron Microscope (SEM) characterization of/CF, as seen from the figure, Co (OH)2The nano-sheets are tightly wrapped in Cu (OH)2And a tubular multistage nano array structure uniformly growing on the surface of the foam copper is formed on the outer wall of the nano wire.
FIG. 2 shows Co (OH) obtained in step B of example 12/Cu(OH)2X-ray diffraction (XRD) characterization of/CF, it can be seen that, in addition to the characteristic diffraction peak of the foam copper substrate (indicated by "□"), Cu (OH) appears2Characteristic diffraction peak of (1) (represented by "△") and Co (OH)2Characteristic diffraction peak (indicated by "four-star"), indicating that the material is composite Co (OH)2/Cu(OH)2a/CF structure. In addition, since Pd/Co (OH)2/Cu(OH)2The Pd loading amount in/CF is small, the material does not have the characteristic diffraction peak of Pd in XRD, and Co (OH)2/Cu(OH)2The characteristic diffraction peaks of the/CF are identical.
FIG. 3 shows Co (OH) obtained in step B of example 22/Cu(OH)2Scanning Electron Microscope (SEM) characterization of/CF, from which it can be seen that Co (OH) is smaller in size2The nano-sheets are tightly wrapped in Cu (OH)2On the outer wall of the nanowire, on the surface of the copper foamForming a more dense tubular multilevel nano-array structure.
FIG. 4 shows Pd/Co (OH) obtained in step C of example 12/Cu(OH)2The Transmission Electron Microscope (TEM) characterization of the/CF shows that after the Pd nanoparticles with ultra-small particle size are uniformly loaded, the overall appearance of the material maintains a hollow tubular structure, the thickness is about 10-15nm, and the width is Co (OH) of 100-250 nm2The nanosheets grown uniformly in Cu (OH)2And (4) the outer wall of the nanowire.
FIG. 5 shows Pd/Co (OH) obtained in step C of example 12/Cu(OH)2High Resolution Transmission Electron Microscopy (HRTEM) characterization of/CF, from which it can be seen that Pd nanoparticles about 2-3nm in diameter are uniformly supported on Co (OH)2The surface of the nano-sheet, the surface material of the lattice stripes with different interplanar spacings in the material is Pd/Co (OH)2/Cu(OH)2a/CF composite structure.
FIG. 6 shows Pd/Co (OH) obtained in step C of example 32/Cu(OH)2High Resolution Transmission Electron Microscopy (HRTEM) characterization of/CF, from which it can be seen that Pd nanoparticles about 6-8nm in diameter are uniformly supported on Co (OH)2And (3) the surface of the nanosheet.
FIG. 7 is a graph of the catalyst cycling performance. When iodobenzene is used as a reactant, Pd/Co (OH)2/Cu(OH)2With 1/CF material, the yield of biphenyl remained 80% after four cycles, indicating Pd/Co (OH)2/Cu(OH)2the/CF has good cycle stability.
The invention has the beneficial effects that: the preparation method adopted by the invention has the advantages of simple and quick conditions, strong operability and easy large-scale production and preparation. The catalytic material prepared by the invention has unique structure and performance advantages, high catalytic activity and stability and high utilization rate of active substances. As the product is used as a heterogeneous catalytic material, the product has the characteristics of convenient recovery and separation, is expected to well solve the problems of low utilization rate of active substances, difficult recovery and the like of the traditional Suzuki reaction catalyst material, and has a certain application prospect in catalytic materials for catalyzing Suzuki reaction to other coupling reactions.
Drawings
FIG. 1 shows Co (OH) obtained in step B of example 12/Cu(OH)2Scanning Electron Microscope (SEM) characterization of/CF.
FIG. 2 shows Co (OH) obtained in step B of example 12/Cu(OH)2X-ray diffraction (XRD) characterization of/CF.
FIG. 3 shows Co (OH) obtained in step B of example 22/Cu(OH)2Scanning Electron Microscope (SEM) characterization of/CF
FIG. 4 shows Pd/Co (OH) obtained in step C of example 12/Cu(OH)2Transmission Electron Microscopy (TEM) characterization of/CF.
FIG. 5 shows Pd/Co (OH) obtained in step C of example 12/Cu(OH)2High Resolution Transmission Electron Microscopy (HRTEM) characterization of/CF.
FIG. 6 shows Pd/Co (OH) obtained in step C of example 32/Cu(OH)2High Resolution Transmission Electron Microscopy (HRTEM) characterization of/CF
FIG. 7 shows Pd/Co (OH) obtained in example 12/Cu(OH)2The recycling performance graph of the/CF catalyst.
Detailed Description
Example 1
A. Preparation of copper hydroxide nanowire array/foam copper precursor
The method comprises the steps of taking copper foam with purity of more than 90% and size of 3 x 4cm as a raw material, and cleaning the copper foam for 3min under ultrasonic by using acetone/ethanol, hydrochloric acid and deionized water respectively.
Weighing 2.28g of ammonium persulfate and 10.0g of sodium hydroxide, dissolving in 100mL of deionized water to prepare a mixed solution, soaking the foamy copper in the mixed solution, reacting at room temperature for 20min, taking out, completely washing with deionized water and ethanol, and drying in an oven at 60 ℃ to obtain Cu (OH)2/CF。
B.Co(OH)2/Cu(OH)2Preparation of/CF precursor
The Cu (OH) prepared in the step A2the/CF was cut into a 1 cm. times.1 cm. times.0.5 mm piece, and used as a working electrode, a Pt mesh as a counter electrode, and an Ag/AgCl electrode (3mol L)-1KCl) as a reference electrode inPerforming electrodeposition at constant voltage of-1.0V in 10mL of electrolyte containing 0.4365g of cobalt nitrate hexahydrate, taking out the deposit for 180s, washing the redundant electrolyte on the surface with deionized water, and drying in an oven at 60 ℃ to obtain Co (OH)2/Cu(OH)2/CF nanotube array, Co (OH)2The nano-sheets are tightly wrapped in Cu (OH)2The surface of the nanowire.
C.Pd/Co(OH)2/Cu(OH)2Preparation of/CF
Weighing 2.94mg of sodium chloropalladate, dissolving in 10mL deionized water to obtain a solution with the concentration of 1mmol/L, and adding Co (OH) in the step B2/Cu(OH)2Soaking the/CF sheet in the solution for reaction for 20min, taking out, thoroughly washing with deionized water, and naturally drying at room temperature to obtain Pd/Co (OH)2/Cu(OH)2a/CF catalyst. Pd nano-particle loaded hollow tubular Pd/Co (OH) with particle size of 2-3nm2/Cu(OH)2a/CF catalyst.
Example 2
A. The procedure is as in example 1
B. Preparation of cobalt hydroxide/copper hydroxide nanotube array/foam copper precursor
Cutting the copper hydroxide nanowire array/the foamy copper prepared in the step B into an electrode slice with the size of 1cm multiplied by 0.5mm, taking the electrode slice as a working electrode, taking a Pt net as a counter electrode, and taking an Ag/AgCl electrode (3mol L)-1KCl) as a reference electrode, constant voltage electrodeposition was carried out for 300s in 10mL of an electrolyte containing 0.2182g of cobalt nitrate hexahydrate, the voltage being-1.0V. Taking out the electrode slice after electrodeposition, removing redundant electrolyte on the surface by deionized water, and drying in a 60 ℃ oven for later use. To obtain Co (OH)2/Cu(OH)2/CF nanotube arrays, slightly smaller Co (OH)2The nano-sheets are tightly wrapped in Cu (OH)2The surface of the nanowire.
C.Pd/Co(OH)2/Cu(OH)2Preparation of/CF
Weighing 2.94mg of sodium chloropalladate, dissolving the sodium chloropalladate in 10mL of deionized water to prepare a solution with the concentration of 1mmol/L, and adding the Co (OH) prepared in the step B2/Cu(OH)2Soaking the/CF nanotube array in the solution at room temperature for reaction for 20minThoroughly washing with deionized water, and naturally drying at room temperature to obtain hollow tubular Pd/Co (OH) loaded with Pd nanoparticles with particle size of 2-3nm2/Cu(OH)2a/CF catalyst.
Example 3
A. Step B the same as in example 1
C.Pd/Co(OH)2/Cu(OH)2Preparation of/CF
Weighing 4.41mg of sodium chloropalladate, dissolving the sodium chloropalladate in 10mL of deionized water to prepare a solution with the concentration of 1.5mmol/L, and adding the Co (OH) prepared in the step B2/Cu(OH)2And soaking the/CF nanotube array at room temperature for reaction for 40min, thoroughly washing with deionized water, and naturally drying at room temperature. Obtaining the hollow tubular Pd/Co (OH) loaded by the Pd nano-particles with the particle size of 6-8nm2/Cu(OH)2a/CF catalytic material.
Application example 1
Suzuki coupling reaction application experiments were performed using the samples prepared in examples 1, 2, and 3 and comparative samples 1, 2, and 3, respectively.
The specific method comprises the following steps:
A. 0.25mmol of iodobenzene, 0.275mmol of phenylboronic acid and 0.50mmol of K2CO3The mixture was added to a 10mL reaction flask and dissolved in 6mL of a 1:1 volume ethanol-water mixture under magnetic stirring. Adding into the mixture with a size of 0.5cm2And it was fixed with a copper wire having a diameter of 0.3 mm.
B. The reaction system continuously reacts for 2 hours at the temperature of 60 ℃, after the reaction is finished, dichloromethane is used for extracting reaction liquid to obtain an organic layer, and anhydrous Na is added2SO4Drying, filtering and rotary evaporating to obtain the final product.
C. And (3) taking the chromatographically pure biphenyl as a standard substance, carrying out external standard method quantification by utilizing High Performance Liquid Chromatography (HPLC), and calculating by a standard curve method to obtain the yield of the biphenyl. The results of determination of the yield of biphenyl are shown in table 1.
TABLE 1 results of Suzuki coupling reactions with different catalysts
Note: comparative samples 1, 2 and 3 are catalysts reported to have excellent performance in the literature, wherein comparative sample 1 is derived from the literature [ appl.surf.Sci.,2017,399:185-191 ]; comparative sample 2 is from the literature [ appl.Catal.A General,2014,473(5):1-6 ]; comparative sample 3 was from the literature [ Langmuir 2017,33:8157-8164 ].
As can be seen from Table 1, the catalyst prepared by the invention is used for the Suzuki reaction from the oriented catalytic reaction of halogenated benzene to biphenyl, when iodobenzene is used as a substrate, the yield of biphenyl can reach more than 99%, and compared with the currently reported catalyst, the catalyst has the advantage that the catalytic efficiency is not lower than that of the existing catalyst under the condition of less active substances. Indicating that the material can be used to catalyze the typical suzuki reaction.
Application example 2
Pd/Co (OH) obtained in example 12/Cu(OH)2The reaction system is used for different types of Suzuki coupling reactions, and the concentration of each substance in the reaction system mixture is as follows: reaction (0.25mmol), phenylboronic acid (0.275mmol), K2CO3(0.5mmol)，EtOH/H2O (1:1,6mL) catalyst (0.06 mol% Pd). The yield analysis of biphenyl and biphenyl derivatives in the product is determined by HPLC and column chromatography respectively. The results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the catalyst of the present invention has generally excellent catalytic effect for various suzuki-miyaura reactions, has considerable advantages with other nano-catalysts, and is expected to be put into practical applications of suzuki-miyaura reactions and other coupling reactions.
Claims (3)
1. A preparation method of a supported palladium multilevel structure catalytic material comprises the following specific steps:
A. ultrasonically cleaning the foamy copper by acetone, ethanol, hydrochloric acid and deionized water for 3-10min respectively, soaking the cleaned foamy copper in a mixed solution of ammonium persulfate with the concentration of 0.05-0.5mol/L and sodium hydroxide with the concentration of 1-5mol/L for 10-40min, cleaning by deionized water, and drying in an oven at the temperature of 60-70 ℃ to obtain copper hydroxide/foamy copper, which is expressed as Cu (OH)2(ii)/CF; wherein Cu (OH)2Is a nanowire array structure;
B. the Cu (OH) obtained in the step A2taking/CF as a working electrode, taking a Pt net or Pt wire electrode as a counter electrode, taking Ag/AgCl as a reference electrode, taking 0.1-0.50 mol/L cobalt nitrate solution as electrolyte, electrodepositing for 100-500 seconds under the condition that the constant potential is-0.5-1.0V, cleaning with deionized water, and drying in an oven at the temperature of 60-70 ℃ to obtain Co (OH)2/Cu(OH)2(ii)/CF; wherein Co (OH)2Is of a nano-sheet structure; due to electrochemical corrosion, Cu (OH)2The structure of (A) is changed from a nano wire into a hollow nano tube;
C. the Co (OH) obtained in step B2/Cu(OH)2placing/CF in 0.002-0.02 mol/L tetrachloropalladate solution to soak for 10-60 min, washing with deionized water, and drying at room temperature to obtain Pd/Co (OH)2/Cu(OH)2and/CF. Wherein Pd is nano-particles with the particle size of 1-5 nm, and is distributed in Co (OH) in a highly dispersed way2The surface of the nanosheet; it is a supported palladium multilevel structure catalytic material.
2. A supported palladium multi-stage structured catalytic material, expressed as Pd/Co (OH), prepared according to the method of claim 12/Cu(OH)2/CF, where CF is a foamed copper substrate, Cu (OH)2For growing nanotubes with hollow structure on CF substrates, Co (OH)2For growth in Cu (OH)2Nanosheets of nanotube outer wall, Pd being highly dispersed in Co (OH)2The nano particles on the surface of the nano sheet have the particle size of 1-5 nm.
3. Use of a supported palladium multi-stage structured catalytic material according to claim 2, which is mainly used for catalyzing Suzuki-Miyaura reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010249291.3A CN111250108A (en) | 2020-04-01 | 2020-04-01 | Supported palladium multilevel structure catalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010249291.3A CN111250108A (en) | 2020-04-01 | 2020-04-01 | Supported palladium multilevel structure catalytic material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111250108A true CN111250108A (en) | 2020-06-09 |
Family
ID=70943510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010249291.3A Withdrawn CN111250108A (en) | 2020-04-01 | 2020-04-01 | Supported palladium multilevel structure catalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111250108A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981483A (en) * | 2021-11-19 | 2022-01-28 | 北京科技大学顺德研究生院 | Preparation method of platinum-doped copper-cobalt hydroxide array structure |
-
2020
- 2020-04-01 CN CN202010249291.3A patent/CN111250108A/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| JIALI LI等: "Uniformly dispersed Pd nanoparticles anchored Co(OH)2/Cu(OH)2 hierarchical nanotube array as high active structured catalyst for Suzuki–Miyaura coupling reactions", 《J MATER SCI》 * |
| 李嘉力: "基于泡沫铜构筑的多级纳米管阵列及其性能研究", 《万方平台》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981483A (en) * | 2021-11-19 | 2022-01-28 | 北京科技大学顺德研究生院 | Preparation method of platinum-doped copper-cobalt hydroxide array structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113371693B (en) | Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof | |
| CN106582887A (en) | Novel catalyst based on metal organic framework material and preparation method and application of novel catalyst | |
| CN102151575B (en) | Method for preparing carbon nanometer tube loaded type catalyst | |
| US11534739B2 (en) | Lignite char supported nano-cobalt composite catalyst and preparation method thereof | |
| CN110813337B (en) | Metal-phosphorus-carbon hierarchical pore catalyst and preparation method and application thereof | |
| CN110947428B (en) | UiO @ Pd @ UiO catalyst and preparation method and application thereof | |
| CN113292733B (en) | Conductive metal organic framework nanorod array composite material and preparation and application thereof | |
| Li et al. | Uniformly dispersed Pd nanoparticles anchored Co (OH) 2/Cu (OH) 2 hierarchical nanotube array as high active structured catalyst for Suzuki–Miyaura coupling reactions | |
| CN113026047A (en) | Method for synthesizing methanol by electrochemically catalyzing and converting carbon dioxide | |
| Zhang et al. | N-Doped porous carbon supported palladium nanoparticles as a highly efficient and recyclable catalyst for the Suzuki coupling reaction | |
| CN111250108A (en) | Supported palladium multilevel structure catalytic material and preparation method and application thereof | |
| CN106475122A (en) | A kind of Ni of low temperature preparation three-dimensional step pore structure2The method of P catalyst | |
| WO2021046998A1 (en) | Palladium-on-carbon catalyst, preparation method therefor, and application thereof | |
| CN107486219A (en) | A kind of preparation method and applications of palladium carried magnetic carbon fiber catalyst | |
| CN111686766B (en) | Metal-fluorine doped carbon composite material, preparation method thereof and application thereof in electrocatalytic nitrogen fixation | |
| CN114381758B (en) | Nickel-doped boehmite and reduced graphene oxide composite electrocatalyst and preparation and application thereof | |
| CN114622227B (en) | Nanometer flake nickel-based electrocatalyst, preparation method and application | |
| CN113463119B (en) | Bismuth-based-silver-based composite material and preparation method and application thereof | |
| CN101774571A (en) | Method for preparing oxide-doped amorphous carbon material | |
| Hu et al. | Carbon Nanotubes-Supported Well-Dispersed Pd Nanoparticles for the Efficiently Selective Hydrogenation of Benzoic Acid to Synthesize Cyclohexane Carboxylic Acid | |
| CN101264882A (en) | Method for preparing carbon nano-tube by using porous Ni3Al alloy as catalyst | |
| Su et al. | Synthesis of Pd/Carbon Hollow Spheres by the Microwave Discharge Method for Catalytic Debenzylation | |
| Yan et al. | 2D Bismuth nanosheet arrays as efficient alkaline hydrogen evolution electrocatalysts | |
| Wang et al. | One-pot synthesis of nickel encapsulated COF-derived catalyst for highly selective and efficient hydrogenation of cinnamaldehyde | |
| CN112774666A (en) | Monoatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde and preparation method thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200609 |