CN112206786A - Multi-metal nanoparticle catalyst and preparation and application thereof - Google Patents
Multi-metal nanoparticle catalyst and preparation and application thereof Download PDFInfo
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- CN112206786A CN112206786A CN202010899731.XA CN202010899731A CN112206786A CN 112206786 A CN112206786 A CN 112206786A CN 202010899731 A CN202010899731 A CN 202010899731A CN 112206786 A CN112206786 A CN 112206786A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000003756 stirring Methods 0.000 claims abstract description 94
- 239000007787 solid Substances 0.000 claims abstract description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 52
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 36
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 32
- 101150003085 Pdcl gene Proteins 0.000 claims description 27
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 22
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 19
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- -1 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene Chemical compound 0.000 claims description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 description 76
- 239000000203 mixture Substances 0.000 description 74
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 239000004576 sand Substances 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229940124543 ultraviolet light absorber Drugs 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/22—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms directly attached to ring nitrogen atoms
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- Chemical Kinetics & Catalysis (AREA)
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- Catalysts (AREA)
Abstract
The invention provides a preparation method of a multi-metal nanoparticle catalyst, which comprises the following steps: (1) pouring alkylamine serving as a capping agent into a container, heating for dissolving, pouring a metal precursor into the container after the alkylamine is completely dissolved, obtaining metal nanoparticles through continuous heating reaction after solids are completely dissolved, then cooling, adding absolute ethyl alcohol for washing, and standing overnight to obtain a mixed solution; (2) pouring activated carbon powder into a closed container, adding deionized water, fully stirring and dispersing, and then pouring hydrogen peroxide, stirring and reacting; pouring the mixed liquid obtained in the step (1) into a container through a constant pressure funnelHeating and stirring in a magnetic stirrer, pouring out the residual liquid after stirring, and putting the residual solid into a vacuum oven for temperature programming and drying to obtain the multi-metal nano particle catalyst. The invention provides the application of the multi-metal nanoparticle catalyst in the reaction shown by the following equation, and the multi-metal nanoparticle catalyst shows high selectivity and high conversion rate.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation of catalysts, and particularly relates to a multi-metal nanoparticle catalyst, a preparation method thereof and application of the catalyst in reduction of 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene into a 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole nitroxide intermediate.
Background
The polymer material is prone to aging phenomena such as brittleness, yellowing and cracking under the irradiation of ultraviolet rays, which can affect the service performance of the polymer material. The benzotriazole ultraviolet light absorber is mainly applied to Polyethylene (PE), Polyformaldehyde (POM) and other polymeric materials due to excellent photochemical stability and other excellent physical properties, and can obviously prolong the service performance.
Benzotriazadols are generally reduced from azo intermediate compounds. The reduction of benzotriazalils can be currently divided into one-step and two-step processes. The so-called one-step process, i.e. the reduction of azo dyes to products with one reducing agent, is a two-step process, i.e. the reduction of dyes to nitrogen oxides with one reducing agent and then the reduction of nitrogen oxide intermediates to the final products with another reducing agent.
The methods for producing benzotriazole ultraviolet light absorbers reported in the literature at present are many and have advantages and disadvantages. Although the technology for synthesizing the benzotriazole ultraviolet light absorber by using the chemical reduction method is mature and the process is simple, the defects of large discharge amount of waste water and waste residue, low atom economic efficiency, expensive reducing agent, high toxicity and the like exist in most cases. The catalytic hydrogenation reduction method has the advantages of small wastewater discharge amount and high atom economy, and hydrogen serving as a reducing agent does not pollute the environment, but the catalytic hydrogenation reduction process is usually accompanied by side reactions to generate a plurality of byproducts, so that the product yield is low and the purity is low, and the industrial application of the technology for synthesizing the benzotriazole ultraviolet light absorbers by the catalytic hydrogenation reduction method is limited.
The supported transition metal, particularly palladium, may catalyze the two-step reaction described above. Modification of the support and active elements, particularly palladium in combination with other metals or ligands, is an important factor affecting the catalytic performance.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of a multi-metal nanoparticle catalyst.
The second technical problem to be solved by the invention is to provide a multi-metal nanoparticle catalyst.
The third technical problem to be solved by the invention is to provide the application of the multi-metal nanoparticle catalyst in the reaction of reducing 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene into a 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole nitroxide intermediate, and the multi-metal nanoparticle catalyst shows high selectivity and high conversion rate.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a multi-metal nanoparticle catalyst, which comprises the following preparation steps:
(1) preparing nano alloy particles: pouring alkylamine serving as a capping agent into a container, heating for dissolving, pouring a metal precursor into the container after the alkylamine is completely dissolved, obtaining metal nanoparticles through continuous heating reaction after solids are completely dissolved, then cooling, adding absolute ethyl alcohol for washing, and standing overnight to obtain a mixed solution; the metal precursor is selected from PdCl2、Cu(NO3)2·3H2O and SnCl4·5H2At least two of O; the carbon number of the alkylamine is 14-16, and the structure of the alkylamine is straight-chain n-alkylamine;
(2) loading of nano alloy particles: pouring activated carbon powder into a closed container, adding deionized water, fully stirring and dispersing, then pouring 3-6 wt% of hydrogen peroxide which is 1-5 times of the mass of the activated carbon, and introducing N2Controlling the pressure in the container to be 0.01-1.0MPa, keeping the temperature at 40-90 ℃ and fully stirring, and intermittently releasing gas in the container during the period until no gas is released in the container any more so as to treat the activated carbon; and (2) pouring the mixed liquid obtained in the step (1) into a container through a constant-pressure funnel, heating and stirring in a magnetic stirrer, pouring out the residual liquid after stirring is finished, and putting the residual solid into a vacuum oven for temperature programmed drying to obtain the multi-metal nanoparticle catalyst.
Preferably, the metal precursor is selected from one of the following: PdCl with the mass ratio of 1:1-32And Cu (NO)3)2·3H2O; the mass ratio is 1: 0.15-0.45 PdCl2And SnCl4·5H2O; (iii) PdCl with the mass percent of 1:1-3:0.15-0.452、Cu(NO3)2·3H2O and SnCl4·5H2O。
Preferably, in the step (1), the mass ratio of the alkylamine to the metal precursor is 90 to 1500: 1.
preferably, the step (1) is specifically carried out as follows: pouring alkylamine into a container, heating to 120 ℃ for dissolving at 100-. When the alkylamine and the metal precursor are dissolved together, sand bath dissolution can be selected, so that the alkylamine and the metal precursor are heated uniformly and stirred magnetically.
Preferably, the mesh number of the activated carbon powder is150-200 mesh, the specific surface area is not less than 800m2Ash content is not higher than 3 wt%, wherein the total content of three metals of iron, aluminum and magnesium is not higher than 0.1 wt% (calculated by metal state).
Preferably, in the step (2), the volume ratio of the activated carbon powder to the deionized water is 1:5 to 10.
Preferably, in the step (2), the feeding mass ratio of the metal to the activated carbon is controlled to be 0.1-1: 100.
Preferably, the magnetic stirring temperature in the step (2) is 30-60 ℃, the stirring speed is 1000-2000rpm, and the stirring is carried out for 2-4 h.
Preferably, the programmed temperature raising procedure in step (2) is: heating to 50-70 deg.C at 1-5 deg.C/min from room temperature, and maintaining for 2-4 h; then raising the temperature from 50-70 ℃ to 110-130 ℃ at the speed of 1-5 ℃/min, and keeping the temperature for 2-4 h.
In a second aspect, the present invention provides a multi-metal nanoparticle catalyst prepared according to the above preparation method.
The catalyst prepared by the invention is composed of a carrier and an active component loaded on the carrier, wherein the active component is a nano alloy particle, and the metal element is selected from at least two of palladium, copper and tin; the carrier is activated carbon with a strong oxidizing group grafted on the surface. The catalyst has the characteristics of high selectivity, high conversion rate and long service life.
In a third aspect, the invention provides an application of the multi-metal nanoparticle catalyst in a reaction of reducing 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene into a 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole oxynitride intermediate.
Further, the application is as follows: putting the multi-metal nanoparticle catalyst into a reaction kettle, putting raw materials of 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene, formamide and toluene into the reaction kettle, wherein the mass ratio of the catalyst to the raw materials is 1:50-100, and the mass ratio of the formamide to the raw materials is 1:1-5, and then reacting for 4-8h at 50-80 ℃ under the condition of hydrogen.
Further, the reaction is carried out under stirring at a rate of not less than 1000 rpm; the hydrogen used is high-purity hydrogen, and the hydrogen pressure is 0.5-2.0 Mpa.
Compared with the prior art, the invention has the following advantages:
1) the preparation method of the catalyst is simple, the operation is easy, and the environmental pollution is small.
2) The composition of the metal active site particles is easy to regulate and control, and the conversion rate and the selectivity performance are high.
Detailed description of the invention
The embodiments of the present invention are described in detail below by way of specific examples, but the scope of the present invention is not limited to the following examples.
The activated carbon is purchased from Fujian Xinsen, is in powder form, has the mesh number of 150-22.5 wt% of ash, wherein the total content of three metals of iron, aluminum and magnesium is 0.05 wt% (calculated by metal state).
Example 1
Weighing 6g of tetradecylamine and 15mg of PdCl2、20.5mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Immediately after that, the temperature was decreased, and 20ml of absolute ethanol was added thereto when the temperature was decreased to 50 ℃ to wash and stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 3 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, and putting the solidPutting into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at a speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 2
Weighing 6g of tetradecylamine and 15mg of PdCl2、20.5mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 120 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 3
Weighing 6g of tetradecylamine and 15mg of PdCl2、41mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, and fully mixingStirring, adding 2ml of 3 wt% hydrogen peroxide, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃, and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 4
Weighing 6g of tetradecylamine and 15mg of PdCl2、41mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 120 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 5
Weighing 6g of tetradecylamine and 15mg of PdCl2、61.5mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all dissolved, weighingGood PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 6
Weighing 6g of tetradecylamine and 15mg of PdCl2、61.5mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 120 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, and setting the program from the roomThe temperature is raised to 70 ℃ at the speed of 5 ℃/min and kept for 4 h; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 7
Weighing 6g of tetradecylamine and 15mg of PdCl2、4.45mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 8
Weighing 6g of tetradecylamine and 15mg of PdCl2、4.45mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 120 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, and controlling the pressure in the container by nitrogenIs 1.0MPa, is kept at the constant temperature of 90 ℃ and is fully stirred. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 9
Weighing 6g of tetradecylamine and 15mg of PdCl2、8.9mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 10
Weighing 6g of tetradecylamine and 15mg of PdCl2、8.9mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 120 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、SnCl4·5H2Pouring O into a three-necked bottle. After the solid is completely dissolved, the temperature is raised from 120 ℃ to 200 DEG CAnd keeping for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 11
Weighing 6g of tetradecylamine and 15mg of PdCl2、13.35mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 12
Weighing 6g of tetradecylamine and 15mg of PdCl2、13.35mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 120 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 13
Weighing 6g of tetradecylamine and 15mg of PdCl2、20.5mgCu(NO3)2·3H2O、4.45mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. Intermittent release during the periodAnd releasing the gas in the container until no gas is released in the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 14
Weighing 6g of tetradecylamine and 15mg of PdCl2、20.5mgCu(NO3)2·3H2O、4.45mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 15
Weighing 6g of tetradecylamine and 15mg of PdCl2、41mgCu(NO3)2·3H2O、8.9mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 16
Weighing 6g of tetradecylamine and 15mg of PdCl2、41mgCu(NO3)2·3H2O、4.45mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixed solution was poured through a constant pressure funnel, and heated and stirred at 60 ℃ and 1000rpm in a magnetic stirrerAnd 4 h. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Example 17
Weighing 6g of tetradecylamine and 15mg of PdCl2、61.5mgCu(NO3)2·3H2O、13.35mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Example 18
Weighing 6g of tetradecylamine and 15mg of PdCl2、61.5mgCu(NO3)2·3H2O、13.35mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. Then the temperature is increasedAnd keeping the temperature at 280 ℃ for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Comparative example 1
Weighing 6g of tetradecylamine and 15mg of PdCl26g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2Pouring into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 5 times that of the activated carbon, fully stirring, then pouring 2ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Comparative example 2
Weighing 6g of tetradecylamine and 15mg of PdCl26g of tetradecylamine are poured into a three-necked flask at 100 ℃The sand bath dissolved in the bottle. After all the PdCl is dissolved, weighing the PdCl2Pouring into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Comparative example 3
Weighing 6g of dodecylamine and 15mg of PdCl26g of dodecylamine were poured into a three-necked flask at 100 ℃ and dissolved in a sand bath. After all the PdCl is dissolved, weighing the PdCl2Pouring into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 100 ℃ to 180 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 0.01MPa by nitrogen, keeping the temperature at 40 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred in a magnetic stirrer at 30 ℃ and 1000rpm for 2 hours. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the productA catalyst.
Comparative example 4
Weighing 6g of octadecylamine and 15mg of PdCl26g of octadecylamine were poured into a three-necked flask at 100 ℃ and dissolved in a sand bath. After all the PdCl is dissolved, weighing the PdCl2Pouring into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to raise the temperature from room temperature to 70 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; then heating from 70 ℃ to 130 ℃ at the speed of 5 ℃/min, keeping for 4h, and drying to obtain the catalyst.
Comparative example 5
Weighing 6g of tetradecylamine and 15mg of PdCl2、61.5mgCu(NO3)2·3H2O、13.35mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2O、SnCl4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon, pouring into the mixed solution, stirring in a magnetic stirrer for 2h, pouring out the residual liquid after stirring is finished, putting the solid into a vacuum oven, setting a program to rise from room temperature to 50 ℃ at 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Comparative example 6
Weighing 6g of tetradecylamine and 15mg of PdCl2、61.5mgCu(NO3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the PdCl is dissolved, weighing the PdCl2、Cu(NO3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 10 min. The temperature was then raised to 260 ℃. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 50 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon, pouring into the mixed solution, stirring in a magnetic stirrer for 2h, pouring out the residual liquid after stirring is finished, putting the solid into a vacuum oven, setting a program to rise from room temperature to 50 ℃ at 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Comparative example 7
Weighing 6g tetradecylamine, 20.5mg Cu (NO)3)2·3H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After the Cu (NO) is completely dissolved, weighing the Cu3)2·3H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Comparative example 8
Weighing 6g tetradecylamine and 4.45mgSnCl4·5H2O, 6g of tetradecylamine were dissolved in a sand bath at 100 ℃ in a three-necked flask. After all the SnCl is dissolved, the SnCl is weighed4·5H2Pouring O into a three-necked bottle. After the solid had dissolved completely, the temperature was raised from 120 ℃ to 200 ℃ and held for 30 min. The temperature was then raised to 280 ℃ and held for 40 min. Then, 20ml of absolute ethanol was added to wash the mixture when the temperature was lowered to 70 ℃ and the mixture was allowed to stand overnight. Weighing 2g of activated carbon powder, pouring the activated carbon powder into a closed container, adding deionized water with the volume 20 times that of the activated carbon, fully stirring, then pouring 10ml of hydrogen peroxide with the concentration of 6 wt%, controlling the pressure in the container to be 1.0MPa by nitrogen, keeping the temperature at 90 ℃ and fully stirring. During the period, the gas in the container is released intermittently until no more gas is released from the container. Then, the obtained mixture was poured through a constant pressure funnel and heated and stirred at 1000rpm for 4 hours at 60 ℃ in a magnetic stirrer. Pouring out the residual liquid after stirring, putting the solid into a vacuum oven, setting the program to rise from room temperature to 50 ℃ at the speed of 1 ℃/min, and keeping for 2 h; then heating from 50 ℃ to 110 ℃ at the speed of 1 ℃/min, keeping for 2h, and drying to obtain the catalyst.
Application examples
Putting the prepared multi-metal nanoparticle catalyst into a reaction kettle, putting raw materials of 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene, formamide and toluene into the reaction kettle, wherein the mass ratio of the catalyst to the raw materials is 1:50, the mass ratio of the formamide to the raw materials is 1:1, and the mass ratio of the toluene to the raw materials is 6:1, stirring and reacting under the condition of 1MPa of hydrogen, the stirring speed is 1000rpm, and the reaction temperature and the reaction time are shown in the table II.
Claims (10)
1. A preparation method of a multi-metal nanoparticle catalyst comprises the following preparation steps:
(1) preparing nano alloy particles: pouring alkylamine serving as a capping agent into a container, heating for dissolving, pouring a metal precursor into the container after the alkylamine is completely dissolved, obtaining metal nanoparticles through continuous heating reaction after solids are completely dissolved, then cooling, adding absolute ethyl alcohol for washing, and standing overnight to obtain a mixed solution; the metal precursor is selected from PdCl2、Cu(NO3)2·3H2O and SnCl4·5H2At least two of O; the carbon number of the alkylamine is 14-16, and the structure of the alkylamine is straight-chain n-alkylamine;
(2) loading of nano alloy particles: pouring activated carbon powder into a closed container, adding deionized water, fully stirring and dispersing, then pouring 3-6 wt% of hydrogen peroxide which is 1-5 times of the mass of the activated carbon, and introducing N2Controlling the pressure in the container to be 0.01-1.0MPa, keeping the temperature at 40-90 ℃ and fully stirring, and intermittently releasing gas in the container during the period until no gas is released in the container any more so as to treat the activated carbon; and (2) pouring the mixed liquid obtained in the step (1) into a container through a constant-pressure funnel, heating and stirring in a magnetic stirrer, pouring out the residual liquid after stirring is finished, and putting the residual solid into a vacuum oven for temperature programmed drying to obtain the multi-metal nanoparticle catalyst.
2. The method of claim 1, wherein: the metal precursor is selected from one of the following: PdCl with the mass ratio of 1:1-32And Cu (NO)3)2·3H2O; the mass ratio is 1: 0.15-0.45 PdCl2And SnCl4·5H2O; (iii) PdCl with the mass percent of 1:1-3:0.15-0.452、Cu(NO3)2·3H2O and SnCl4·5H2O。
3. The method of claim 1, wherein: in the step (1), the mass ratio of the alkylamine to the metal precursor is 90-1500: 1.
4. the method of claim 1, wherein: the step (1) is specifically implemented as follows: pouring alkylamine into a container, heating to 120 ℃ for dissolving at 100-.
5. The method of claim 1, wherein: the mesh number of the activated carbon powder is 150-200 meshes, and the specific surface area is not less than 800m2The ash content is not higher than 3 wt%, wherein the total content of three metals of iron, aluminum and magnesium is not higher than 0.1 wt%.
6. The method of claim 1, wherein: the conditions of heating and stirring in the magnetic stirrer in the step (2) are as follows: the magnetic stirring temperature is 30-60 ℃, the stirring speed is 1000-2000rpm, and the stirring time is 2-4 h.
7. The method of claim 1, wherein: the procedure of the programmed temperature rise in the step (2) is as follows: heating to 50-70 deg.C at 1-5 deg.C/min from room temperature, and maintaining for 2-4 h; then raising the temperature from 50-70 ℃ to 110-130 ℃ at the speed of 1-5 ℃/min, and keeping the temperature for 2-4 h.
8. A multi-metallic nanoparticle catalyst prepared according to the preparation method of claim 1.
9. The use of the multi-metal nanoparticle catalyst of claim 8 in the reaction of reducing 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene to 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole nitroxide intermediate;
10. the use of claim 9, wherein: the application specifically comprises the following steps: putting the multi-metal nanoparticle catalyst into a reaction kettle, putting raw materials of 2-nitro- (2 '-hydroxy-5' -methylphenyl) azobenzene, formamide and toluene into the reaction kettle, wherein the mass ratio of the catalyst to the raw materials is 1:50-100, and the mass ratio of the formamide to the raw materials is 1:1-5, and then reacting for 4-8h at 50-80 ℃ under the condition of hydrogen.
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