CN111905835A - Preparation method and application of efficient photo-thermal catalytic material - Google Patents
Preparation method and application of efficient photo-thermal catalytic material Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 44
- 229920001690 polydopamine Polymers 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 17
- 229960004643 cupric oxide Drugs 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000007983 Tris buffer Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims description 11
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 241000530268 Lycaena heteronea Species 0.000 claims description 5
- 238000006701 autoxidation reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
Abstract
The invention relates to a preparation method of an efficient photothermal catalytic material, a copper oxide-polydopamine-palladium (CuO-PDA-Pd) efficient photothermal catalytic material obtained by the preparation method, and application of the efficient photothermal catalytic material in catalyzing Suzuki reaction. Compared with the noble metal-palladium catalyst in the prior art, the copper oxide-polydopamine-palladium catalyst prepared by the method has lower production cost and is suitable for large-scale popularization. The copper oxide-polydopamine-palladium catalyst prepared by the method is used for catalyzing Suzuki coupling reaction, after the reaction is carried out for 90 min, the conversion rate reaches 90%, and the conversion efficiency is high.
Description
Technical Field
The invention relates to a catalyst material, in particular to a high-efficiency photo-thermal catalytic material which can be used as a catalyst for Suzuki reaction and applied to the field of organic synthesis.
Background
In recent years, noble metal nanoparticles such as gold, silver, etc. have been recognized as a novel effective material for collecting sunlight, because they have high light absorptivity in a wide spectrum range of sunlight including visible light and ultraviolet rays. When the noble metal nanoparticles are used in catalytic reactions, both plasma photocatalysis and photothermal heating contribute to catalytic activity. The current reports have utilized noble metal alloys, such as gold-palladium, as photo-thermal catalytic materials. Noble metal-palladium bimetallic, although highly catalytic, has a very high cost and complex synthesis process that has hindered its practical application. Reducing the cost of the catalyst is key to facilitating its use. Recently, copper oxide (CuO) has been found to be one of the superior photo-thermal materials. Thus, copper oxide is a promising catalyst support with a high inventory and a low cost compared to noble metals.
In view of the above, there is a need to develop a new photothermal catalytic material with low cost and high efficiency.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a high-efficiency photo-thermal catalytic material, which comprises the following steps:
step (1), copper sulfate pentahydrate (CuSO) is taken4·5H2Dissolving O) in water, heating to 50-60 deg.C under stirring, maintaining the temperature, adding sodium hydroxide (NaOH) solution, heating to 65-75 deg.C, maintaining the temperature to obtain blue copper hydroxide (Cu (OH)2）；
Step (2), adding D-glucose into the solution obtained in the step (1), and keeping the temperature of the mixture solution at 65-75 ℃; the color of the suspension gradually changed to red; centrifuging to obtain red precipitate cuprous oxide (Cu)2O), washing with water and ethanol sequentially for several times;
step (3), dispersing the cuprous oxide obtained in the step (2) in NaOH solution, preserving for autoxidation, collecting a product copper oxide (CuO), and washing with water and ethanol for several times in sequence;
step (4), mixing the Tris buffer solution, the copper oxide and the Polydopamine (PDA) under stirring, stirring the mixture to obtain a product copper oxide-polydopamine (CuO-PDA), and washing for a plurality of times;
step (5), dispersing the product copper oxide-polydopamine (CuO-PDA) obtained in the step (4) in deionized water, and adding potassium tetrachloropalladate (K)2PdCl4) Solution, stirring, and then dropwise addingSodium borohydride (NaBH)4) And (3) stirring the solution for reaction, centrifuging after the reaction is finished to obtain a product copper oxide-polydopamine-palladium (CuO-PDA-Pd), fully rinsing with water and ethanol, and drying in a reduced pressure dryer to obtain the copper oxide-polydopamine-palladium (CuO-PDA-Pd).
As a preferable technical scheme, in the step (1), 0.63-2.5 g of copper sulfate pentahydrate is dissolved in 50 mL of deionized water, and 1.25 g of copper sulfate pentahydrate is more preferably dissolved in 50 mL of deionized water. The concentration of the NaOH solution is 2.5-3.5M, and the addition amount is 20-40 mL; more preferably, the concentration is 3M and the amount added is 30 mL. Preferably, the stirring speed is 300 rpm, the heating temperature is 55 ℃, and the holding time is 2 min. As a preferred technical scheme, the NaOH solution is added and heated to 70 ℃, and the heat preservation time is 5 min.
As a preferable technical scheme, in the step (2), 0.2-0.4 g D-glucose is added into the solution obtained in the step (1), and the more preferable adding amount is 0.3 g of D-glucose. As a preferable technical scheme, the temperature for heat preservation is 70 ℃, and the time for heat preservation is 20 min. Preferably, the number of washing is 3.
As a preferable technical scheme, in the step (3), the concentration of the NaOH solution is 0.05-0.15M, and the preferable concentration is 0.1M. Preferably, the autoxidation time is 20-28 h, more preferably 24 h. As a preferred technical scheme, the washing times are 4 to 5.
As a preferable technical scheme, in the step (4), the pH value of the Tris buffer solution is 8.2-8.8, and 0.2-0.3 g of blue vitriol and 350-450 mu L of hydrogen peroxide are dissolved in each 100 mL of the Tris buffer solution; more preferably, the pH is 8.5, and 0.25 g of copper sulfate pentahydrate and 398. mu.L of hydrogen peroxide (H) are dissolved in 100 mL of Tris buffer2O2）。
As a preferred technical scheme, in the step (4), 40-60 mg of copper oxide and 40-60 mg of polydopamine are mixed in each 100 mL of Tris buffer. Preferably, 50mg of copper oxide and 50mg of polydopamine are mixed.
As a preferable technical scheme, in the step (4), the stirring speed is 400-600 rpm, and the more preferable stirring speed is 500 rpm; the stirring time is 5-15 min, and the more preferable stirring time is 10 min.
As a preferred technical scheme, in the step (5), 15-25 mg of copper oxide-polydopamine is dispersed in 30-50 mL of deionized water; more preferably, 20 mg of copper oxide-polydopamine is dispersed in 40 mL of deionized water. The concentration of the potassium tetrachloropalladate solution is 4-6 mM, and the addition amount is 3.5-4 mL; more preferably, the concentration of the potassium tetrachloropalladate solution is 5 mM, and the addition amount is 3.77 mL; followed by stirring for 5 min.
As a preferable technical scheme, in the step (5), the concentration of the sodium borohydride solution is 2-3 mM, and the addition amount is 35-45 mL; preferably at a concentration of 2.5 mM, 40 mL is added dropwise; the dropwise addition time was 30 min, followed by stirring for 3 h. Preferably, the drying time is 24 hours.
The high-efficiency photothermal catalytic material prepared by the invention consists of three parts (CuO-PDA-Pd) consisting of copper oxide, polydopamine and nano palladium. Copper oxide, as a p-type semiconductor with a narrow band gap (overall volume of 1.2 eV), is a material with great application prospects in the manufacture of solar cells due to its high absorbance, low thermal emissivity, relatively good electrical properties and high carrier concentration. Various organic-inorganic nanocomposite materials having high thermal conductivity, high electrical conductivity, high mechanical strength and high temperature durability can also be prepared using nano-scale copper oxide.
Polydopamine can adhere to almost all surfaces of materials, including precious metals, metal oxides, semiconductors, ceramics, and synthetic polymers. Polydopamine has been used in various catalytic systems and as a catalyst support due to its general binding ability. Polydopamine is reactive towards noble metal ions, making metal catalyst nanoparticles (e.g., gold, silver, and palladium) susceptible to in situ deposition. At the same time, polydopamine films can also be grown on virtually all substrates. In combination with these two unique functions, the catalytic metal nanoparticles can be attached to any particle or substrate with the aid of a polydopamine interlayer. And polydopamine as a catalyst carrier does not influence the catalytic performance of the supported catalyst.
The metal palladium is a commonly used catalyst and is commonly used for various organic synthesis reactions, particularly the nano palladium which has higher catalytic efficiency due to higher specific surface area.
For the reasons, the invention provides a preparation method of a copper oxide-polydopamine-palladium catalyst material and a copper oxide-polydopamine-palladium composite catalyst prepared by the method. The catalyst has excellent catalytic effect on Suzuki reaction at room temperature.
The invention also aims to provide a copper oxide-polydopamine-palladium (CuO-PDA-Pd) high-efficiency photothermal catalytic material prepared by the method.
Another object of the present invention is to provide a use of the above copper oxide-polydopamine-palladium (CuO-PDA-Pd) high efficiency photothermal catalytic material, which is used as a catalyst for Suzuki reaction.
The beneficial technical effects of the invention are as follows:
(1) according to the invention, copper oxide is used as a carrier of the catalyst, the palladium catalyst is loaded by preparing copper oxide-polydopamine, and compared with the precious metal-palladium catalyst in the prior art, the prepared copper oxide-polydopamine-palladium catalyst has lower production cost and is suitable for large-scale popularization.
(2) The copper oxide-polydopamine-palladium catalyst prepared by the method is used for catalyzing Suzuki coupling reaction, and after the reaction is carried out for 90 min, the conversion rate reaches 90%, and the conversion efficiency is high.
Drawings
FIG. 1 is an SEM image of CuO-PDA-Pd obtained by the preparation in example 1 of the present invention.
FIG. 2 is an EDX analysis of CuO-PDA-Pd as prepared in example 1 of the present invention.
FIG. 3 is a picture of elemental analysis of CuO-PDA-Pd as obtained in example 1 of the present invention.
FIG. 4 shows a Suzuki reaction system using a xenon lamp as a light source.
Detailed Description
The invention is further described below with reference to specific embodiments and the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A preparation method of a high-efficiency photo-thermal catalytic material comprises the following steps:
dissolving 1.25 g of blue copper sulfate pentahydrate in 50 mL of water, stirring at a stirring speed of 300 rpm, heating to 55 ℃, keeping the temperature for 2 min, adding 30 mL of NaOH solution, quickly setting the temperature to 70 ℃, and keeping the temperature for 5 min to generate blue copper hydroxide; the concentration of the NaOH solution was 3M.
Step (2), adding 0.3 g D-glucose into the solution obtained in the step (1), and keeping the temperature of the mixture solution at 70 ℃ for about 20 min; the color of the suspension gradually changed to red; centrifuging to obtain red precipitate cuprous oxide, and washing the red precipitate with water and ethanol for 3 times.
Step (3), dispersing the cuprous oxide obtained in the step (2) in a NaOH solution, preserving for 24 h for autoxidation, collecting a product cupric oxide, and washing for 3 times by using water and ethanol in sequence; the concentration of the NaOH solution was 0.1M.
Step (4), mixing 100 mL of Tris buffer solution, 50mg of copper oxide and 50mg of polydopamine at a stirring speed of 500 rpm, stirring the mixture for 10 min to obtain a product copper oxide-polydopamine, and washing the product copper oxide-polydopamine for 3 times; the pH value of the Tris buffer solution is 8.5, and 0.25 g of blue vitriol and 398 mu L of hydrogen peroxide are dissolved in each 100 mL of the Tris buffer solution.
And (5) dispersing 20 mg of the product copper oxide-polydopamine obtained in the step (4) in 40 mL of deionized water, adding 3.77 mL of 5 mM potassium tetrachloropalladate solution, stirring for about 5 min, then dropwise adding 40 mL of 2.5 mM sodium borohydride solution, stirring for reaction for 3 h, centrifuging after the reaction is finished to obtain the product copper oxide-polydopamine-palladium (CuO-PDA-Pd), fully rinsing with water and ethanol, and drying in a reduced pressure dryer for 24 h to obtain the copper oxide-polydopamine-palladium (CuO-PDA-Pd).
The CuO-PDA-Pd composite catalytic material synthesized in example 1 was characterized. The results of the characterization are shown in fig. 1 to 3. In which fig. 1 is an SEM image, fig. 2 is an EDX analysis, and fig. 3 is an elemental analysis picture.
It can be seen from fig. 1 to 3 that palladium has been successfully supported on the copper oxide-polydopamine carrier. In fig. 2, the black dots distributed on the surface of the copper oxide-polydopamine carrier are palladium.
Test example
The CuO-PDA-Pd prepared in example 1 was selected as a catalyst, and the catalytic activity for the Suzuki coupling reaction under xenon lamp irradiation was evaluated.
The reaction system is shown in fig. 4, and the Suzuki coupling reaction is performed under the irradiation of a xenon lamp. The Suzuki coupling reaction was performed using bromobenzene and phenylboronic acid. The reaction formula is shown as the following formula (1):
The reaction steps are as follows: bromobenzene (8.4 muL, 0.08 mmol), phenylboronic acid (10.9 mg, 0.08 mmol), deionized water (1.5 mL), NaOH (10 mg, 0.25 mmol), cetyltrimethylammonium bromide (CTAB, 36 mg) and CuO-PDA-Pd catalyst (2 mg) were placed in a quartz cuvette with an optical path of 1 cm, irradiated with a continuous Xenon Lamp (model: Xenon Oriel Arc Lamp, Mod.67005, Newport, UK; maximum optical power: 300W), the reaction was stirred at 1000 rpm for 20 min, 30 min, 60 min, 90 min, and the reaction temperature was room temperature (25 ℃).
The effect of the catalytic reaction is shown in table 1 below:
table 1: conversion of bromobenzene under xenon lamp irradiation in the presence of CuO-PDA-Pd catalyst for different reaction times
| Reaction time (min) | 20 | 30 | 60 | 90 |
| Conversion (%) | 32.8 | 57.8 | 79.9 | 90.0 |
The results in Table 1 show that the conversion of the Suzuki coupling reaction reached 90% after 90 min of reaction.
The invention provides a novel preparation method of a photo-thermal catalytic material and the photo-thermal catalytic material prepared by the preparation method, the material has high catalytic efficiency and lower cost compared with a noble metal catalytic material, and is suitable for large-scale popularization.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The preparation method of the high-efficiency photo-thermal catalytic material is characterized by comprising the following steps of:
dissolving blue copper sulfate pentahydrate in water, heating to 50-60 ℃ under stirring, preserving heat, adding NaOH solution, heating to 65-75 ℃, preserving heat, and generating blue copper hydroxide;
step (2), adding D-glucose into the solution obtained in the step (1), and keeping the temperature of the mixture solution at 65-75 ℃; the color of the suspension gradually changed to red; centrifuging to obtain red precipitate cuprous oxide, and washing with water and ethanol sequentially for several times;
step (3), dispersing the cuprous oxide obtained in the step (2) in a NaOH solution, preserving for autoxidation, collecting the product cupric oxide, and washing with water and ethanol for several times in sequence;
step (4), mixing the Tris buffer solution, the copper oxide and the polydopamine under stirring, stirring the mixture to obtain a product copper oxide-polydopamine, and washing for a plurality of times;
and (5) dispersing the product copper oxide-polydopamine obtained in the step (4) in deionized water, adding a potassium tetrachloropalladate solution, stirring, then dropwise adding a sodium borohydride solution, stirring for reaction, centrifuging after the reaction is finished to obtain the product copper oxide-polydopamine-palladium, fully rinsing with water and ethanol, and drying in a reduced pressure dryer to obtain the copper oxide-polydopamine-palladium.
2. The method for preparing a high efficiency photothermal catalytic material according to claim 1, wherein: in the step (1), 1.25 g of blue vitriod is dissolved in 50 mL of deionized water; the concentration of the NaOH solution is 3M, and the addition amount is 30 mL; stirring speed is 300 rpm, heating temperature is 55 ℃, and heat preservation time is 2 min; adding NaOH solution, heating to 70 deg.C, and keeping the temperature for 5 min.
3. The method for preparing a high efficiency photothermal catalytic material according to claim 1, wherein: in the step (2), 0.3 g D-glucose is added into the solution obtained in the step (1), the heat preservation temperature is 70 ℃, and the heat preservation time is 20 min; the number of washes was 3.
4. The method for preparing a high efficiency photothermal catalytic material according to claim 1, wherein: in the step (3), the concentration of the NaOH solution is 0.1M; the autoxidation time is 24 hours; the number of washing times is 4-5 times.
5. The method for preparing a high efficiency photothermal catalytic material according to claim 1, wherein: in the step (4), the pH value of the Tris buffer solution is 8.5, and 0.25 g of blue vitriol and 398 mu L of hydrogen peroxide are dissolved in each 100 mL of the Tris buffer solution.
6. The method for preparing a high efficiency photothermal catalytic material according to claim 5, wherein: in the step (4), 50mg of copper oxide and 50mg of polydopamine are mixed in every 100 mL of Tris buffer solution; the stirring speed was 500 rpm and the stirring time was 10 min.
7. The method for preparing a high efficiency photothermal catalytic material according to claim 1, wherein: in the step (5), 20 mg of copper oxide-polydopamine is dispersed in 40 mL of deionized water; the concentration of the potassium tetrachloropalladate solution is 5 mM, and the addition amount is 3.77 mL; followed by stirring for 5 min.
8. The method for preparing a high efficiency photothermal catalytic material according to claim 7, wherein: in the step (5), the concentration of the sodium borohydride solution is 2.5 mM, and the dropwise addition amount is 40 mL; then stirring and reacting for 3 hours; the drying time was 24 h.
9. The high efficiency photothermal catalytic material prepared by the method of any one of claims 1 to 8.
10. Use of the high efficiency photothermal catalytic material according to claim 9, wherein: the application is as a catalyst of Suzuki reaction.
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| CN202010889678.5A CN111905835B (en) | 2020-08-28 | 2020-08-28 | Preparation method and application of efficient photo-thermal catalytic material |
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| CN113121998A (en) * | 2021-04-13 | 2021-07-16 | 河南科技大学 | Copper-based composite material, preparation method and application thereof in field of photo-thermal conversion |
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