CN114534721B - Preparation method and application of Au@Pd core-shell structure super-long nanowire in water phase - Google Patents
Preparation method and application of Au@Pd core-shell structure super-long nanowire in water phase Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 73
- 239000011258 core-shell material Substances 0.000 title claims abstract description 44
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 50
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- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 34
- 235000010323 ascorbic acid Nutrition 0.000 claims description 17
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- 239000011668 ascorbic acid Substances 0.000 claims description 17
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 claims description 16
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- 239000002243 precursor Substances 0.000 description 5
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- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- -1 imidazole cations Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 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
- 231100000719 pollutant Toxicity 0.000 description 1
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- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Abstract
The invention relates to a preparation method and application of an Au@Pd core-shell structured ultra-long nanowire in a water phase, a certain amount of 1-hexadecyl-3-methylimidazole chloride ionic liquid aqueous solution is taken and added into a round-bottom flask, and HAuCl is sequentially added into the round-bottom flask 4 ，Na 2 PdCl 4 KBr; uniformly mixing the reactants to obtain a reaction solution; adding a reducing agent with a certain concentration into the reaction solution, uniformly mixing, and standing at 30 ℃ for reaction for 8-10h to prepare a reaction mixture; and (3) centrifugally separating the reaction mixture, taking out the lower layer of sediment, centrifugally washing, and vacuum drying to obtain the product which is the Au@Pd core-shell structure ultra-long nanowire. The invention adopts the ionic liquid and KBr to jointly regulate the morphology, structure and catalytic performance of the product, and the reaction is nontoxic and green. The prepared Au@Pd is an ultra-long nanowire with a core-shell structure, and has very high catalytic activity and selectivity for the catalytic oxidation and conversion of p-hydroxybenzaldehyde into p-hydroxybenzaldehyde.
Description
Technical Field
The invention relates to the technical field of preparation of bimetallic nano materials, in particular to a preparation method and application of an Au@Pd core-shell structure super-long nanowire in a water phase, wherein the Au@Pd core-shell structure super-long nanowire is prepared in an aqueous solution under a mild condition through the assistance of ionic liquid, and the application of the Au@Pd core-shell structure super-long nanowire in the aspect of catalytic oxidation of p-hydroxybenzyl alcohol is researched.
Background
Compared with other bimetallic nanomaterials, the Au-Pd bimetallic nanomaterials have wider application due to higher activity. For example, au-Pd catalysts have been used in the commercial synthesis of vinyl acetate, which is synthesized in the united states alone under Au-Pd catalysis at 480 ten thousand tons per year. Au-Pd nano material is also widely applied to surface enhanced Raman scattering, CO low-temperature oxidation and H-based nano material 2 And O 2 Direct synthesis of H 2 O 2 The fields of hydrodechlorination of Cl-containing pollutants in industrial wastewater, hydrodesulphurization of S-containing organic matters, electro-oxidation of formic acid, oxidation of alcohols into aldehydes, heck coupling reaction, selective hydrogenation and the like. Compared with single metal Pd, after the Au element is introduced, electrons of Pd are transferred to Au, so that the Pd has partial electropositivity. In addition, the lattice mismatch of Au and Pd will affect the bond length of the pd—pd bond, resulting in the d-band center of Pd being far from the fermi level. Thus, the electron transfer and bond length changes enhance the atomic nature of the Pd species and enhance its catalytic activity and selectivity.
The Chinese patent of the application number 202010591708.4 synthesizes the graphene oxide supported Au-Pd catalyst which has higher catalytic activity and stability in the coupling reaction. In the invention, firstly, the carrier graphene oxide needs to be prepared, then the dropping speed of the carrier solution in the precursor solution needs to be strictly controlled under ultrasound, then the temperature is increased to 80-90 ℃ by an oil bath heating program under a certain rotating speed, and then NaBH is added dropwise 4 The aqueous solution is introduced into the reaction system. It can be seen that the catalyst needs to be prepared step by step, has more strict operation conditions, and uses a carrier and more expensive NaBH 4 A reducing agent.
Thus, there is a need to develop Au-Pd nano-particles with simpler operating conditions and less expensive reagentsOne-pot preparation technology of rice material. Moreover, the catalytic activity of the nanomaterial is closely related to not only the characteristics of the metal element itself but also the size, morphology, crystal phase, structure, and the like thereof. The linear nano material has the characteristics of larger specific surface area and self-support, can stably exist without support of a carrier, is not easy to agglomerate in the catalytic application process, has higher activity, and is convenient to recycle. Chinese patent application No. 202010828021.8 uses HAuCl 4 And Pd (acac) 2 And preparing Au-Pd alloy nano-wires by taking triisopropylsilane as a reducing agent in normal hexane solution under the auxiliary action of oleylamine at 45 ℃. Which is at CO 2 Has excellent catalytic activity in the electro-reduction reaction. However, the reaction is carried out in an organic solvent, a metal organic precursor is also needed, and the reducing agent is also an organic substance, so that the cost is increased, and the atmospheric pollution is brought. Therefore, the development of a simple, mild and green one-step Au-Pd nanowire synthesis technical route is particularly important.
Disclosure of Invention
The invention aims to provide a preparation method and application of an Au@Pd core-shell structure ultra-long nanowire in a water phase, wherein water is used as a reaction medium, and ionic liquid 1-hexadecyl-3-methylimidazole chloride ([ C ] is adopted 16 mim]Cl) and KBr are used for jointly regulating the morphology, structure and catalytic performance of the product, and a weak reducing agent ascorbic acid is used for reducing Au and Pd metal precursors, so that the reaction is nontoxic and green. The prepared Au@Pd is an ultra-long nanowire with a core-shell structure, the average diameter of the nanowire is about 48nm, the length of the nanowire reaches tens of micrometers, and the nanowire has very high catalytic activity and selectivity for the catalytic oxidation and conversion of p-hydroxybenzaldehyde into p-hydroxybenzaldehyde.
The invention aims at providing a preparation method of an Au@Pd core-shell structure super-long nanowire in a water phase, which specifically comprises the following steps:
(1) Weighing a certain amount of ionic liquid 1-hexadecyl-3-methylimidazole chloride salt to prepare an ionic liquid aqueous solution for later use;
(2) Adding a certain volume of ionic liquid aqueous solution into a round-bottom flask;
(3) Adding HAuCl into the round bottom flask in the step (2) 4 Adding Na 2 PdCl 4 Finally adding KBr; fully and uniformly mixing the reactants to obtain a reaction solution;
(4) Preparing a reducing agent with a certain concentration, and adding the reducing agent into the reaction solution obtained in the step (3); gently shaking the round-bottom flask to uniformly mix reactants, and then standing at 30 ℃ for reaction for 8-10h to prepare a reaction mixture;
(5) And (3) centrifugally separating the reaction mixture prepared in the step (4), removing supernatant to obtain a lower-layer precipitate, centrifugally washing the precipitate by using high-purity water, and then drying in vacuum at 40-60 ℃ for 24 hours to obtain the product, namely the Au@Pd core-shell structured ultra-long nanowire.
In the preparation method, the molar concentration of the 1-hexadecyl-3-methylimidazole chloride salt in the ionic liquid aqueous solution in the step (1) is 0.025-0.10M. The addition amount of the ionic liquid aqueous solution in the step (2) is 5mL.
Further, HAuCl in step (3) 4 、Na 2 PdCl 4 The amount of KBr added substances is 0.002-0.004mmol, 0.001-0.003mmol and 0.004-0.005mmol respectively.
Further, the reducing agent in the step (4) is an aqueous solution of ascorbic acid with a molar concentration of 0.1-0.2M; the addition amount of the reducing agent was 0.5mL.
The invention also aims to provide the Au@Pd core-shell structure super-long nanowire obtained by the preparation method, the average diameter of the nanowire is about 48nm, the length of the nanowire is very long and can reach tens of micrometers, the nanowire is formed by orderly assembling and welding and growing small nano particles which are generated in advance, and the growth mode causes a large number of defects of the nanowire, so that the nanowire is beneficial to improving the catalytic activity of the nanowire. The outside of the nanowire has more Pd element, and the inside is mainly Au element.
The invention also examines the catalytic application of the prepared Au@Pd core-shell structured ultra-long nanowire as a catalyst for catalyzing and oxidizing p-hydroxybenzaldehyde into p-hydroxybenzaldehyde:
the prepared Au@Pd core-shell structure is subjected to ultra-long nano0.005mmol of rice noodle is dispersed in 1mL of water, evenly mixed by ultrasonic, and then added into 9mL of water containing p-hydroxybenzyl alcohol and K 2 CO 3 To obtain a mixed solution, wherein the mixed solution comprises p-hydroxybenzyl alcohol and K 2 CO 3 Molar concentrations of 25mM and 75mM, respectively. Then the reaction is carried out in an oxygen atmosphere at 60 ℃ and under normal pressure, the reaction liquid is quenched by dilute hydrochloric acid, extracted by ethyl acetate for three times and anhydrous Na is adopted 2 SO 4 After drying, the product was analyzed by gas chromatography-mass spectrometry.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method adopts water as a reaction medium and adopts ionic liquid 1-hexadecyl-3-methylimidazole chloride ([ C) 16 mim]Cl) and KBr together regulate the morphology, structure and catalytic performance of the product. The ionic liquid consists of anions and cations, and imidazole cations [ C ] 16 mim] + AuCl as precursor 4 - And PdCl 4 2- The anions have electrostatic interactions. Meanwhile, the imidazole ring also has certain interaction with the metal element. And compared with the common surfactant cetyl trimethyl ammonium bromide, the cetyl trimethyl ammonium bromide has weaker acting force, so that the cetyl trimethyl ammonium bromide is favorable for cleaning in the post-treatment process, and a product with a 'clean' surface is obtained. Anion Br - Has a certain adsorption effect with metal species. Therefore, the application of the ionic liquid and KBr is expected to regulate and synthesize the bimetallic nano material with uniform morphology and higher catalytic activity.
2. In the invention, the weak reducing agent ascorbic acid is adopted in the aqueous solution to reduce the Au and Pd metal precursors, and the reaction is nontoxic and green.
3. The preparation technical route of the Au@Pd core-shell structure ultra-long nanowire does not need to use a surfactant or a hard template, and does not need high temperature, high pressure, special reaction equipment, organic solvents, reagents and the like. The reaction is carried out at 30 ℃, the reaction condition is mild, the reaction is static, stirring is not needed, the operation is simple, the reaction is green, and the energy consumption is low.
4. The average diameter of the Au@Pd core-shell structure ultra-long nanowire prepared by the method is about 48nm, and the length of the nanowire is very long and can reach tens of micrometers. The scanning electron microscope and the transmission electron microscope with different magnifications can clearly observe a large number of prepared Au@Pd core-shell structure ultra-long nanowires, and the diameters of the nanowires are very uniform. Because the length of the nanowire is too long and exceeds the shooting area of a transmission electron microscope, accurate measurement is not available, and the preliminary judgment can reach tens of micrometers. By carefully examining photographs of the product taken by transmission electron microscopy, it was found that the black and white contrast was not uniform along each nanowire, as well as the local diameters were slightly different. It is inferred from this that nanowires are grown from ordered assembly fusion of pre-generated small nanoparticles. This growth mode results in a large number of defects in the nanowires, which are beneficial for improving the catalytic activity thereof. Meanwhile, the long linear structure enables the catalyst to have the characteristic of self-supporting, and the original structure of the catalyst can be maintained in catalytic application, so that the catalyst is not easy to gather and deactivate. And the support of a carrier is not needed, and the reaction is convenient to recycle after the reaction is finished. The HAADF-STEM graph and the element surface scanning graph show that the nano wire has more Pd elements outside and mainly Au elements inside, and the prepared Au@Pd nano wire has a core-shell structure.
5. The selectivity of the Au@Pd core-shell structured ultra-long nanowire prepared by the method for catalytic oxidation of the p-hydroxybenzaldehyde to the p-hydroxybenzaldehyde is up to 100%, the reaction can be completed within 50min, the conversion rate of the p-hydroxybenzaldehyde is 100%, the whole reaction process is carried out in an aqueous solution at 60 ℃ under normal pressure, the safety and the energy consumption are low, and the catalyst consumption is low, so that the prepared Au@Pd core-shell structured ultra-long nanowire catalyst has very good catalytic activity and selectivity for oxidation of the p-hydroxybenzaldehyde.
Drawings
FIG. 1 is an SEM image at 5000 times magnification of Au@Pd ultralong nanowires prepared in example 3;
FIG. 2 is an SEM image at a magnification of 100000 times of the Au@Pd ultralong nanowires prepared in example 3;
FIG. 3 is a TEM image of Au@Pd ultralong nanowires prepared in example 3, magnified 40000 times;
FIG. 4 is a HAADF-STEM and elemental surface scanning of the Au@Pd ultralong nanowires prepared in example 3;
FIG. 5 is a graph showing the conversion rate of the Au@Pd ultralong nanowire catalytic oxidation p-hydroxybenzyl alcohol prepared in example 3 with time.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
A preparation method of an Au@Pd core-shell structure ultra-long nanowire in a water phase comprises the following steps:
step one, weighing a certain amount of 1-hexadecyl-3-methylimidazole chloride ([ C) 16 mim]Cl) to prepare an ionic liquid aqueous solution with the molar concentration of 0.025-0.10M for standby;
step two, adding 5mL of the ionic liquid aqueous solution obtained in the step one into a round-bottom flask;
step three, firstly adding HAuCl with the mass of 0.002-0.004mmol into the round bottom flask of the step two 4 Adding Na with the amount of 0.001-0.003mmol 2 PdCl 4 Finally adding KBr with the mass of 0.004-0.005 mmol; fully and uniformly mixing the reactants to obtain a reaction solution;
weighing ascorbic acid, adding distilled water to prepare an aqueous solution of the ascorbic acid with the molar concentration of 0.1-0.2M, and adding a certain volume of the aqueous solution of the ascorbic acid into the reaction solution obtained in the step three; gently shaking the round-bottom flask to uniformly mix the reaction solution, and then standing at 30 ℃ for reaction for 8-10h to prepare a reaction mixture;
and fifthly, centrifugally separating the reaction mixture prepared in the step four, removing supernatant to obtain lower-layer sediment, centrifugally washing the sediment for 4-6 times by high-purity water, and then vacuum drying at 40-60 ℃ for 24 hours to obtain the product, namely the Au@Pd core-shell structured ultra-long nanowire.
Example 1:
1) Weighing a certain amount ofIonic liquid [ C ] 16 mim]Cl, constant volume to 100mL, is prepared into [ C with 0.10M molar concentration 16 mim]An aqueous Cl solution;
2) Take 5mL of [ C ] in step 1) 16 mim]Aqueous Cl solution into round bottom flask;
3) To the round-bottomed flask of step 2) was initially charged HAuCl in an amount of 0.003mmol 4 Then Na (0.002 mmol) was added 2 PdCl 4 Finally adding KBr with the mass of 0.004 mmol; fully and uniformly mixing the reactants to obtain a reaction solution;
4) Weighing ascorbic acid, adding distilled water to prepare an aqueous solution of ascorbic acid with the molar concentration of 0.1M, and adding 0.5mL into the reaction solution in the step 3); gently shaking the round-bottom flask to uniformly mix the reaction solution, and then standing at 30 ℃ for reaction for 10 hours to prepare a reaction mixture;
5) And (3) centrifugally separating the reaction mixture prepared in the step (4), removing supernatant to obtain lower-layer sediment, centrifugally washing the lower-layer sediment for 6 times by using high-purity water, and vacuum drying at 40 ℃ for 24 hours to obtain the final product, namely the Au@Pd core-shell structured ultra-long nanowire.
Example 2:
1) Weighing a certain amount of ionic liquid [ C ] 16 mim]Cl, constant volume to 100mL, is prepared into [ C ] with 0.080M molar concentration 16 mim]An aqueous Cl solution;
2) Take 5mL of [ C ] in step 1) 16 mim]Aqueous Cl solution into round bottom flask;
3) To the round-bottomed flask of step 2) was initially charged HAuCl in an amount of 0.004mmol 4 Further adding Na in an amount of 0.001mmol 2 PdCl 4 Finally adding KBr with the amount of 0.005 mmol; fully and uniformly mixing the reactants to obtain a reaction solution;
4) Weighing ascorbic acid, adding distilled water to prepare an aqueous solution of ascorbic acid with the molar concentration of 0.2M, and adding 0.5mL into the reaction solution in the step 3); gently shaking the round-bottom flask to uniformly mix the reaction solution, and then standing at 30 ℃ for reaction for 9 hours to prepare a reaction mixture;
5) And (3) centrifugally separating the reaction mixture prepared in the step (4), removing supernatant to obtain lower-layer sediment, centrifugally washing the lower-layer sediment for 6 times by using high-purity water, and vacuum drying at 60 ℃ for 24 hours, wherein the finally obtained product is the Au@Pd core-shell structured ultra-long nanowire.
Example 3:
1) Weighing a certain amount of ionic liquid [ C ] 16 mim]Cl, to a volume of 100mL, formulated to a molar concentration of 0.025M [ C ] 16 mim]An aqueous Cl solution;
2) Take 5mL of [ C ] in step 1) 16 mim]Aqueous Cl solution into round bottom flask;
3) To the round-bottomed flask of step 2) was initially charged HAuCl in an amount of 0.003mmol 4 Further adding Na in an amount of 0.001mmol 2 PdCl 4 Finally, KBr with the amount of substances of 0.0045mmol is added; fully and uniformly mixing the reactants to obtain a reaction solution;
4) Weighing ascorbic acid, adding distilled water to prepare an aqueous solution of ascorbic acid with the molar concentration of 0.125M, and adding 0.5mL into the reaction solution in the step 3); gently shaking the round-bottom flask to uniformly mix the reaction solution, and then standing at 30 ℃ for reaction for 8 hours to prepare a reaction mixture;
5) And (3) centrifugally separating the reaction mixture prepared in the step (4), removing supernatant to obtain lower-layer sediment, centrifugally washing the lower-layer sediment for 5 times by using high-purity water, and vacuum drying at 50 ℃ for 24 hours to obtain the final product, namely the Au@Pd core-shell structured ultra-long nanowire.
Fig. 1 to 3 are SEM images and TEM images of the au@pd core-shell structured ultra-long nanowires prepared in this example, and a large amount of au@pd prepared by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) with different magnifications can be clearly observed to be ultra-long nanowires, and the diameters of the ultra-long nanowires are very uniform. The average diameter is about 48nm after measurement, the length is very long and exceeds the shooting area of a transmission electron microscope, so that accurate measurement is not available, and the preliminary judgment can reach tens of micrometers. By carefully examining photographs of the product taken by transmission electron microscopy, it was found that the black and white contrast was not uniform along each nanowire, as well as the local diameters were slightly different. It is inferred from this that nanowires are grown from ordered assembly fusion of pre-generated small nanoparticles. This growth mode results in a large number of defects in the nanowires, which are beneficial for improving the catalytic activity thereof. Meanwhile, the long linear structure has the characteristic of self-supporting, the original structure of the catalyst can be maintained in catalytic application, aggregation and inactivation are not easy, the support of a carrier is not needed, and the catalyst is convenient to recycle after the reaction is finished.
Fig. 4 is a HAADF-STEM and element surface scanning diagram of the ultra-long nano wire with the au@pd core-shell structure prepared in this embodiment, and it can be seen from the figure that the outer part of the nano wire has more Pd elements and the inner part is mainly Au element, so that it can be proved that the Au-Pd nano wire has a core-shell structure.
Dispersing 0.005mmol of the Au@Pd core-shell structured ultra-long nanowire prepared in the embodiment in 1mL of water, uniformly mixing by ultrasonic, and adding the mixture into 9mL of water containing p-hydroxybenzyl alcohol and K 2 CO 3 To obtain a mixed solution, wherein the mixed solution comprises p-hydroxybenzyl alcohol and K 2 CO 3 Molar concentrations of 25mM and 75mM, respectively. Then the reaction is carried out in an oxygen atmosphere at 60 ℃ and under normal pressure, the reaction liquid is quenched by dilute hydrochloric acid, extracted by ethyl acetate for three times and anhydrous Na is adopted 2 SO 4 After drying, the product is analyzed by adopting a gas chromatograph-mass spectrometer, and the change of the conversion rate of the Au@Pd core-shell structure ultra-long nanowire catalytic oxidation p-hydroxybenzyl alcohol with time is examined, and the result is shown in figure 5. According to the graph, the selectivity of the Au@Pd core-shell structured ultra-long nanowire for catalytic oxidation of the p-hydroxybenzaldehyde to the p-hydroxybenzaldehyde is up to 100%, the reaction can be completed within 50min, the conversion rate of the p-hydroxybenzaldehyde is 100%, the whole reaction process is carried out in an aqueous solution at 60 ℃ under normal pressure, the safety and the energy consumption are low, and the catalyst consumption is low, so that the prepared Au@Pd core-shell structured ultra-long nanowire catalyst has good catalytic activity and selectivity for the oxidation of the p-hydroxybenzaldehyde.
Example 4:
1) Weighing a certain amount of ionic liquid [ C ] 16 mim]Cl, constant volume to 100mL, is prepared into [ C ] with the molar concentration of 0.050M 16 mim]An aqueous Cl solution;
2) Step of taking 5mL1) Middle [ C ] 16 mim]Aqueous Cl solution into round bottom flask;
3) To the round-bottomed flask of step 2) was initially charged HAuCl in an amount of 0.003mmol 4 Na was added in an amount of 0.003mmol 2 PdCl 4 Finally adding KBr with the mass of 0.004 mmol; fully and uniformly mixing the reactants to obtain a reaction solution;
4) Weighing ascorbic acid, adding distilled water to prepare an aqueous solution of ascorbic acid with the molar concentration of 0.15M, and adding 0.5mL into the reaction solution in the step 3); gently shaking the round-bottom flask to uniformly mix the reaction solution, and then standing at 30 ℃ for reaction for 9 hours to prepare a reaction mixture;
5) And 4) centrifugally separating the reaction mixture prepared in the step 4), removing supernatant to obtain lower-layer sediment, centrifugally washing the lower-layer sediment for 4 times by using high-purity water, and vacuum drying at 40 ℃ for 24 hours to obtain the final product, namely the Au@Pd core-shell structured ultra-long nanowire.
Example 5:
1) Weighing a certain amount of ionic liquid [ C ] 16 mim]Cl, constant volume to 100mL, is prepared into [ C with 0.06M molar concentration 16 mim]An aqueous Cl solution;
2) Take 5mL of [ C ] in step 1) 16 mim]Aqueous Cl solution into round bottom flask;
3) To the round-bottomed flask of step 2) was initially charged HAuCl in an amount of 0.002mmol 4 Further adding Na in an amount of 0.001mmol 2 PdCl 4 Finally adding KBr with the mass of 0.004 mmol; fully and uniformly mixing the reactants to obtain a reaction solution;
4) Weighing ascorbic acid, adding distilled water to prepare an aqueous solution of ascorbic acid with the molar concentration of 0.10M, and adding 0.5mL into the reaction solution in the step 3); gently shaking the round-bottom flask to uniformly mix the reaction solution, and then standing at 30 ℃ for reaction for 10 hours to prepare a reaction mixture;
5) And (3) centrifugally separating the reaction mixture prepared in the step (4), removing supernatant to obtain lower-layer sediment, centrifugally washing the lower-layer sediment for 6 times by using high-purity water, and vacuum drying at 50 ℃ for 24 hours to obtain the final product, namely the Au@Pd core-shell structured ultra-long nanowire.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (5)
1. The application of the Au@Pd core-shell structure super-long nanowire in the water phase in the catalytic oxidation of p-hydroxybenzaldehyde to the conversion of p-hydroxybenzaldehyde is characterized in that the preparation method of the Au@Pd core-shell structure super-long nanowire in the water phase specifically comprises the following steps:
(1) Weighing a certain amount of ionic liquid 1-hexadecyl-3-methylimidazole chloride salt to prepare an ionic liquid aqueous solution, wherein the molar concentration of the 1-hexadecyl-3-methylimidazole chloride salt in the ionic liquid aqueous solution is 0.025-0.10M for later use;
(2) Adding a certain volume of ionic liquid aqueous solution into a round-bottom flask;
(3) Adding HAuCl into the round bottom flask in the step (2) 4 Adding Na 2 PdCl 4 Finally adding KBr; fully and uniformly mixing the reactants to obtain a reaction solution;
(4) Preparing an ascorbic acid aqueous solution with the molar concentration of 0.1-0.2 and M as a reducing agent, and adding the aqueous solution into the reaction solution obtained in the step (3); gently shaking the round-bottom flask to uniformly mix reactants, and then standing at 30 ℃ to react for 8-10h to prepare a reaction mixture;
(5) And (3) centrifugally separating the reaction mixture prepared in the step (4), discarding supernatant to obtain a lower-layer precipitate, centrifugally washing the precipitate with high-purity water, and then vacuum drying at 40-60 ℃ to obtain an Au@Pd core-shell structure super-long nanowire, wherein the Au@Pd core-shell structure super-long nanowire is formed by orderly assembling, welding and growing small pre-generated nano particles, and is used for catalyzing and oxidizing p-hydroxybenzaldehyde to be converted into p-hydroxybenzaldehyde.
2. The use of the ultra-long nanowire with the au@pd core-shell structure in the aqueous phase according to claim 1 for catalyzing and oxidizing p-hydroxybenzaldehyde to p-hydroxybenzaldehyde, wherein the addition amount of the ionic liquid aqueous solution in the step (2) is 5mL.
3. The use of the ultra-long nanowires of au@pd core-shell structure in aqueous phase according to claim 1 or 2 for the catalytic oxidation of p-hydroxybenzyl alcohol to p-hydroxybenzaldehyde, characterized by HAuCl in step (3) 4 、Na 2 PdCl 4 The amount of KBr added substances is 0.002-0.004mmol, 0.001-0.003mmol and 0.004-0.005mmol respectively.
4. Use of the ultra-long nanowires of au@pd core-shell structure in aqueous phase according to claim 1 or 2 for catalytic oxidation of p-hydroxybenzaldehyde to p-hydroxybenzaldehyde, characterized by the addition of a reducing agent in an amount of 0.5mL.
5. The use of the ultra-long nanowires of au@pd core-shell structure in aqueous phase according to claim 1 for the catalytic oxidation of p-hydroxybenzaldehyde to p-hydroxybenzaldehyde, wherein the average diameter of the ultra-long nanowires of au@pd core-shell structure is 48 nm.
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