CN116173946A - Gold catalyst for efficiently converting benzyl alcohol under alkali-free condition and rich in defect sites, preparation method and application - Google Patents
Gold catalyst for efficiently converting benzyl alcohol under alkali-free condition and rich in defect sites, preparation method and application Download PDFInfo
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000010931 gold Substances 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 46
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000007547 defect Effects 0.000 title claims abstract description 15
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 5
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000004075 alteration Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 230000002431 foraging effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000010146 3D printing Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical group [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- -1 zinc magnesium aluminum Chemical compound 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention belongs to the technical field of fine chemical synthesis and catalytic material application, and discloses a gold catalyst for efficiently converting benzyl alcohol into a defect-rich site under an alkali-free condition, a preparation method and application. Adopting MgAl-LDH hydrotalcite as a carrier, and in the process of anchoring an Au precursor to the LDH carrier, reducing the Au precursor in situ by adjusting the acid-alkali property on the surface of the LDH, and generating the Au nano-sheet with the 2D structure, the surface of which is rich in defect sites. The average particle size of gold in the catalyst is 3.0-3.8nm, the Au active site is fully exposed, the surface dispersity is as high as 40.9-43.0%, and a Au-LDH strong interaction interface is formed. Can rapidly catalyze and convert benzyl alcohol in a low temperature region of 50-80 ℃ and in an alkali-free environment, the conversion rate is close to 100% at 80 ℃, and the selectivity of the benzaldehyde can reach 100%. The catalyst disclosed by the invention is simple to prepare, does not need high-temperature roasting, saves energy and is strong in stability.
Description
Technical Field
The invention discloses an Au/LDH catalyst rich in defect sites, a preparation method and application thereof, which can be used for preparing aldehydes by efficiently catalyzing and converting benzyl alcohol under the mild condition without alkali, and belongs to the technical fields of fine chemical synthesis and catalytic material application.
Background
The oxidation of benzyl alcohol to benzaldehyde is a typical alcohol oxidation reaction, wherein benzaldehyde is an important fine chemical intermediate, and is widely applied to the fields of medicines, dyes, fragrances and the like. The conventional benzaldehyde preparation method has a toluene chlorination method, but the method needs to introduce chlorine gas to chlorinate toluene side chains in the preparation process, so that the application of the method is limited due to the introduction of the chlorine gas. Another method is benzyl alcohol oxidation, which is often added with strong oxidants such as potassium dichromate and potassium permanganate, but the introduction of heavy metal ions is not in accordance with the green development requirements, which results in less than optimal process conditions. The oxygen is taken as an important clean energy to replace the strong oxidant, so the invention adopts the oxygen as the oxidant, and the benzyl alcohol and the oxygen are utilized to generate benzaldehyde through oxidation reaction, other byproducts can not appear in the process, and the process is simple and environment-friendly.
Patent CN113322477 discloses a method for preparing benzaldehyde by oxidizing benzyl alcohol in a 3D printing flow electrochemical reactor. The method prepares a flowing electrochemical reactor by a 3D printing technology and prepares a 3D printing nickel electrode by an electroplating method. The design of the reactor can increase the contact between the reaction liquid and the electrodes, has higher specific surface area and reduces the requirement of the catalyst, but needs to carry out the reaction for preparing benzaldehyde by selectively oxidizing benzyl alcohol under alkaline condition. The method is easy to cause environmental pollution, corrode equipment and the like, and cannot be used as a long-term benzyl alcohol oxidation method.
In order to avoid the problems of environmental pollution and the like caused by adding alkaline substances in the oxidation reaction. The efficient and stable catalyst invention has become a significant aspect of the oxidation of benzyl alcohol to benzaldehyde. The supported gold catalyst has become a research hot spot in heterogeneous catalytic reaction, can be applied to various catalytic reaction systems, such as selective oxidation of alcohols, selective oxidation of olefin, catalytic combustion of methane, water vapor conversion and other reactions, and has great relation with the catalytic activity of the catalyst not only related to factors such as the size, electronic structure, particle morphology and the like of gold particles, but also related to the properties of the carrier. LDH (layered double hydroxide) is a solid with strong alkalinity, a layered structure and an excellent specific surface area, and its main plate is composed of divalent and trivalent metal cations, exchangeable anions and water molecules exist between the plate layers, and has component controllability, and a great number of alkaline sites are provided around each metal ion with abundant hydroxyl functional groups, which is beneficial to promotion of oxidative dehydrogenation, and is often used as a catalyst carrier.
Patent CN102773097 discloses a preparation method of a supported bimetallic nano catalyst. The bimetallic nano particles loaded with different palladium and gold contents by the magnesium aluminum hydrotalcite are used as catalysts and applied to benzyl alcohol oxidation to benzaldehyde. The catalyst has high catalytic activity and good stability, and is suitable for the oxidation reaction of alcohol in water phase. However, the catalyst has long preparation period, high preparation temperature and high catalyst consumption, and potential safety hazard is easily caused.
Patent CN105435787 discloses a preparation method of a high-dispersion supported nano gold catalyst. The zinc magnesium aluminum spinel ZnMgAl with high dispersion and high specific surface area is prepared by a one-step hydrothermal-reduction method 2 O loads nano gold catalyst. The increase of the alkaline position is realized by regulating and controlling the acid-base property of the surface of the carrier, and the carrier is applied to the reaction for preparing benzaldehyde by selectively oxidizing benzyl alcohol. The nano Au catalyst has novel and unique structure and strong stability. However, the reaction environment is alkaline, the reaction is carried out under the pressure of 0.1-0.2 MPa, the process is complex, and the danger coefficient is high.
In view of the above, it is important to develop a catalyst with high efficiency, which uses LDH as a carrier to load Au nanoparticles, to realize the efficient catalytic oxidation of benzyl alcohol and molecular oxygen to generate benzaldehyde at normal pressure, no alkali and lower temperature.
Disclosure of Invention
The invention aims to provide a gold catalyst which is applied to defect-rich sites for efficiently converting benzyl alcohol under alkali-free conditions, a preparation method and application. The preparation process is simple, mgAl-LDH hydrotalcite is adopted as a carrier, and the 2D structure Au nano-sheet with the surface rich in defect positions (including step positions, kinks and inflection points) is generated. The Au active site in the catalyst is fully exposed, and the surface dispersity is as high as 40.9-43.0%. The catalyst can be used for preparing benzaldehyde by high-efficiency catalytic conversion of benzyl alcohol under mild alkali-free conditions.
The technical scheme of the invention is as follows:
the gold catalyst for high-efficiency conversion of benzyl alcohol under alkali-free condition has MgAl-LDH hydrotalcite as carrier, and the material contains great amount of alkali sites and hydroxyl functional groups and may be used as the dominant carrier for alkali-free catalytic oxidation of benzyl alcohol. Au is used as an active component of the catalyst, and is a 2D structure Au nano-sheet with the surface rich in defect sites (including step sites, kinks and inflection points), and an Au precursor is loaded on the LDH surface by a precipitation reduction method, and the loading amount is controlled to be 1.5wt% of the carrier. The formation of gold nanoparticle defect sites can be regulated and controlled by changing the magnesium-aluminum atomic ratio of LDH. Can efficiently catalyze and oxidize benzyl alcohol to prepare benzaldehyde under the condition of no alkali and normal pressure. The Au active site in the catalyst is fully exposed, and the surface dispersity is as high as 40.9-43.0%. The average particle size of the gold active component is 3.0-3.8nm.
A preparation method of a gold catalyst for efficiently converting a defect-rich site of benzyl alcohol under an alkali-free condition comprises the following steps:
(1) Preparation of LDH: 0.1875mol/L of Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O mixed solution in which Mg (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The mass ratio of the O is 2:1-4:1, and the O is marked as solution A; 0.425mol/L NaOH and Na are prepared again 2 CO 3 Mixing solution, wherein, naOH and Na 2 CO 3 The mass ratio of the substances is 2.4:1, which is marked as solution B; dripping A, B solution into water at a volume ratio of 1:1 under stirring by using a coprecipitation method, keeping the pH value of the process to be 9.0, then placing the solution in an oil bath at 80 ℃ for ageing for 12 hours, cooling to room temperature, and performing suction filtration, washing and drying to obtain white LDH solid powder;
(2) Preparation of LDH-loaded Au nanoparticle catalyst:
to a concentration of 5.08×10 -2 Adding 0.12mol/L urea solution into the chloroauric acid solution, wherein the mass ratio of urea to chloroauric acid substances is 400:1; after fully mixing, adding LDH solid into the mixed solution, stirring for 6 hours at 80 ℃, cooling to room temperature, adding 0.1mol/L sodium borohydride solution, wherein the mass ratio of sodium borohydride to chloroauric acid is 10:1, continuously stirring for 2 hours at room temperature, filtering after the completion, washing with deionized water until the filtrate is neutral, and drying for 8 hours in a 60 ℃ drying box.
The catalyst is applied to preparing benzaldehyde by oxidizing benzyl alcohol, and comprises the following specific steps:
benzyl alcohol, paraxylene and Au/LDH catalyst are mixed, the mass ratio of the paraxylene to the benzyl alcohol is 100:1, and the mass ratio of the benzyl alcohol to active metal Au in the catalyst is 440:1. At 80 ℃ and normal pressure, 20mL/min of oxygen is introduced for continuous reaction for 4 hours. And detecting the composition and content of the substances of the system by adopting gas chromatography.
The invention has the beneficial effects that:
1. in the process of anchoring the Au precursor to the LDH carrier, the Au precursor is reduced in situ by adjusting the acid alkalinity of the LDH surface, and a 2D structure Au nano-sheet with the surface rich in defect sites (including ladder sites, kinks and inflection points) is generated.
2. Regulating the proportion of magnesium and aluminum in LDH promotes preferential growth of LDH (015) crystal faces, and Au atoms migrate to form an interacted Au-LDH interface due to lattice matching effect of LDH (015) and Au (111).
3. According to the method provided by the invention, the worth of series catalysts show excellent catalytic performance in benzyl alcohol selective oxidation reaction, the benzyl alcohol conversion rate is nearly 100% under the optimized condition, the selectivity of the benzaldehyde is 100%, and the application prospect is very wide.
Drawings
FIG. 1 is Au/Mg prepared in examples 1-4 x X-ray diffraction pattern of Al-LDH catalyst.
FIG. 2 is Au/Mg prepared in example 1 3.5 Transmission electron microscopy spectra of Al-LDH catalysts.
FIG. 3 is Au/Mg prepared in example 1 3.5 Spherical aberration correction scanning electron microscopy of Au particles in Al-LDH catalysts.
FIG. 4 is Au/Mg prepared in example 1 3.5 Spherical aberration correction scanning electron microscopy of Au particles in Al-LDH catalysts.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1
Firstly, 0.0116mol of Mg (NO) 3 ) 2 ·6H 2 O solid and 0.00333mol of Al (NO) 3 ) 3 ·9H 2 The O solid was added to a beaker containing 80mL of deionized water and noted as solution A; another 0.96g NaOH solids and 1.06g Na were taken 2 CO 3 The solid was added to a 80mL beaker of deionized water and noted as solution B; the two beakers are placed into an ultrasonic instrument for ultrasonic oscillation for 2 minutes to fully dissolve and uniformly disperse the solid. Then the two solutions are respectively poured into two constant pressure funnels and are fixed on an iron stand. Another 250mL beaker was taken, 50mL deionized water was poured into it as a mother liquor and placed on a stirrer. Firstly, opening a piston of a constant pressure funnel for holding the solution B, dripping the solution B until the pH value becomes 9, then opening a piston for holding the solution A and dripping the solution B together, keeping the pH value of the two mixed solutions to be constant at 9, and dripping at an average rate of 2 drops per second. The liquid in the 250mL beaker was found to become increasingly turbid with a white precipitate appearing. After the solution was consumed, the resulting liquid was transferred to a three-necked flask and placed in an 80 ℃ oil bath for aging for 12h. After the completion, cooling to room temperature, suction filtering, washing with deionized water to neutrality. Drying in an oven at 60 ℃ for 12 hours. Grinding to obtain Mg 3.5 Al-LDH carrier.
Will be 5.08X10 -2 HAuCl in mol/L 4 0.6mL of the solution was removed, and 10mL of deionized water was added thereto and stirred, and 0.73g of urea was measured and dissolved in 20mL of deionized water, and poured into the single-necked flask. This was moved to an 80℃oil bath and stirred for 6 hours, then cooled to room temperature and 3mL of a 0.1mol/L sodium borohydride solution was added thereto for reduction for 2 hours. Filtering, and washing to neutrality. Placing in a drying oven at 60 ℃ for 8 hours. Grinding processGrinding to obtain Au/Mg 3.5 Al-LDH catalyst. Wherein the average particle diameter of the Au particles is 3.0nm.
Benzyl alcohol catalytic oxidation reaction, adding 20mg of catalyst, 0.0629mol/L benzyl alcohol solution 8mL into a 25mL three-neck flask, continuously introducing 20mL/min of oxygen after connecting a reaction device, introducing a condensing tube for condensation reflux, starting stirring, continuously reacting for 4 hours under normal pressure, wherein the benzyl alcohol conversion rate is close to 100%, and the benzaldehyde selectivity is 100%.
For the Au/Mg obtained x XRD characterization of Al-LDH catalyst, au/Mg can be seen from FIG. 1 x Characteristic diffraction peaks of the (003), (006), (012), (015), (018), (110) and (113) crystal faces appear on the spectrum of the Al-LDH, and the appearance of the characteristic diffraction peaks represents that the characteristic diffraction peaks are hydrotalcite structures (PDF#14-0191), which indicate that the LDH is successfully synthesized by the method. In addition, the LDH (015) crystal face remained intact and had a high crystallinity, and the lattice size matched to that of the Au (111) face was 98%. FIG. 2 is a transmission electron microscopic image of the catalyst of example 1, in which Au nanoparticles were uniformly dispersed on the surface of the support, which was found to be 3.0nm by counting the Au particle size. Fig. 3 is a spherical aberration correcting scanning electron micrograph of the catalyst of example 1, in which abnormal arrangement of boundary Au atoms, having an unusual spherical structure, was observed, and a large number of irregular 2D gold nanoflakes having step and corner positions were present, indicating the formation of defective Au particles on LDH carriers. FIG. 4 shows the spherical aberration correcting electron microscope image of the catalyst of example 1, showing migration of Au atoms to Mg 3.5 In the Al-LDH lattice, delocalized gold atoms are induced to form with metal surface defects and a strong Au-LDH interaction interface is formed. In combination with the analytical characterization results, since the successfully synthesized LDH carrier provides enough alkaline sites for benzyl alcohol catalytic oxidation reaction to realize catalytic oxidation of benzyl alcohol under alkali-free condition, the average size of Au particles is small and uniformly dispersed, the dispersity is as high as 43.0%, which promotes efficient conversion of benzyl alcohol on Au active sites, and furthermore, in this example 1, due to formation of Au nano-sheets with 2D structure rich in defective sites on the strong interaction interface of Au-LDH and formed delocalizationAu atoms, the formation of which exposes more active sites, favors the adsorption and activation of reactant molecules, and thus promotes the catalytic oxidation of benzyl alcohol to benzaldehyde.
Example 2
Firstly, 0.01125mol of Mg (NO 3 ) 2 ·6H 2 O solid and 0.00375mol of Al (NO) 3 ) 3 ·9H 2 The O solid was added to a beaker containing 80mL of deionized water and noted as solution A; another 0.96g NaOH solids and 1.06g Na were taken 2 CO 3 The solid was added to a 80mL beaker of deionized water and noted as solution B; the two beakers are placed into an ultrasonic instrument for ultrasonic oscillation for 2 minutes to fully dissolve and uniformly disperse the solid. Then the two solutions are respectively poured into two constant pressure funnels and are fixed on an iron stand. Another 250mL beaker was taken and 50mL deionized water was poured into it as mother liquor and placed on a stirrer. Firstly, opening a piston of a constant pressure funnel for holding the solution B, dripping the solution B until the pH value becomes 9, then opening a piston for holding the solution A and dripping the solution B together, keeping the pH value of the two mixed solutions to be constant at 9, and dripping at an average rate of 2 drops per second. The liquid in the 250mL beaker was found to become increasingly turbid with a white precipitate appearing. After the solution was consumed, the resulting liquid was transferred to a three-necked flask and placed in an 80 ℃ oil bath for aging for 12h. After the completion, cooling to room temperature, suction filtering, washing with deionized water to neutrality. Drying in an oven at 60 ℃ for 12 hours. Grinding to obtain Mg 3 Al-LDH carrier.
Will be 5.08X10 -2 HAuCl in mol/L 4 0.6mL of the solution was removed, and 10mL of deionized water was added thereto and stirred, and 0.73g of urea was measured and dissolved in 20mL of deionized water, and poured into the single-necked flask. This was moved to an 80℃oil bath and stirred for 6 hours, then cooled to room temperature and 3mL of a 0.1mol/L sodium borohydride solution was added thereto for reduction for 2 hours. Filtering, and washing to neutrality. Placing in a drying oven at 60 ℃ for 8 hours. Grinding to obtain Au/Mg 3 Al-LDH catalyst. Wherein the average particle diameter of the Au particles is 3.8nm.
Benzyl alcohol catalytic oxidation reaction, adding 15mg of catalyst, 0.0629mol/L benzyl alcohol solution 8mL into a 25mL three-neck flask, wherein the solvent is paraxylene, continuously introducing 20mL/min of oxygen after the reaction device is installed, introducing a condensing tube for condensation reflux, starting stirring, and continuously reacting for 4 hours under normal pressure, wherein the benzyl alcohol conversion rate reaches 82.8%, and the benzaldehyde selectivity is 96.7%.
Since the average particle diameter of the Au particles of the catalyst was 3.8nm, the dispersity was 40.9%, and the dispersity was smaller as compared with that of Au particles in example 1, which was larger. From fig. 1, it is understood that the (015) crystal plane intensity is weaker in the catalyst of this example, resulting in a decrease in the Au-LDH interaction intensity, so that it is inferior to the catalytic activity of the catalyst of example 1.
Example 3
Firstly, 0.0107mol of Mg (NO) 3 ) 2 ·6H 2 O solid and 0.00428mol of Al (NO) 3 ) 3 ·9H 2 The O solid was added to a beaker containing 80mL of deionized water and noted as solution A; another 0.96g NaOH solids and 1.06g Na were taken 2 CO 3 The solid was added to a 80mL beaker of deionized water and noted as solution B; the two beakers are placed into an ultrasonic instrument for ultrasonic oscillation for 2 minutes to fully dissolve and uniformly disperse the solid. Then the two solutions are respectively poured into two constant pressure funnels and are fixed on an iron stand. Another 250mL beaker was taken and 50mL deionized water was poured into it as mother liquor and placed on a stirrer. Firstly, opening a piston of a constant pressure funnel for holding the solution B, dripping the solution B until the pH value becomes 9, then opening a piston for holding the solution A and dripping the solution B together, keeping the pH value of the two mixed solutions to be constant at 9, and dripping at an average rate of 2 drops per second. The liquid in the 250mL beaker was found to become increasingly turbid with a white precipitate appearing. After the solution was consumed, the resulting liquid was transferred to a three-necked flask and placed in an 80 ℃ oil bath for aging for 12h. After the completion, cooling to room temperature, suction filtering, washing with deionized water to neutrality. Drying in an oven at 60 ℃ for 12 hours. Grinding to obtain Mg 2.5 Al-LDH carrier.
Will be 5.08X10 -2 HAuCl in mol/L 4 0.6mL of the solution was removed, and 10mL of deionized water was added thereto and stirred, and 0.73g of urea was measured and dissolved in 20mL of deionized water, and poured into the single-necked flask. This was moved to an 80℃oil bath and stirred for 6 hours, then cooled to room temperature and 3mL of a 0.1mol/L sodium borohydride solution was added thereto for reduction for 2 hours. Filtering, and washing to neutrality. Placing in a drying oven at 60 ℃ for 8 hours. Grinding processGrinding to obtain Au/Mg 2.5 Al-LDH catalyst. Wherein the average particle diameter of the Au particles is 3.4nm.
Benzyl alcohol catalytic oxidation reaction, adding 30mg of catalyst, 0.0629mol/L benzyl alcohol solution 8mL into a 25mL three-neck flask, wherein the solvent is paraxylene, continuously introducing 20mL/min of oxygen after the reaction device is installed, introducing a condensing tube for condensation reflux, starting stirring, continuously reacting for 4 hours under normal pressure, wherein the benzyl alcohol conversion rate reaches 93.1%, and the benzaldehyde selectivity is 96.4%.
Since the average particle diameter of the Au particles of the catalyst was 3.4nm, the Au particles were larger in size than in example 1. As can be seen from fig. 1, the (015) crystal face strength of the catalyst of this example is the weakest, resulting in reduced Au-LDH interaction strength, and it is difficult to form Au nanoparticles rich in defective sites, and the number of exposed active sites is small, so that the catalytic activity is inferior to that of example 1.
Example 4
Firstly, 0.012mol of Mg (NO) 3 ) 2 ·6H 2 O solid and 0.003mol of Al (NO) 3 ) 3 ·9H 2 The O solid was added to a beaker containing 80mL of deionized water and noted as solution A; another 0.96g NaOH solids and 1.06g Na were taken 2 CO 3 The solid was added to a 80mL beaker of deionized water and noted as solution B; the two beakers are placed into an ultrasonic instrument for ultrasonic oscillation for 2 minutes to fully dissolve and uniformly disperse the solid. Then the two solutions are respectively poured into two constant pressure funnels and are fixed on an iron stand. Another 250mL beaker was taken and 50mL deionized water was poured into it as mother liquor and placed on a stirrer. Firstly, opening a piston of a constant pressure funnel for holding the solution B, dripping the solution B until the pH value becomes 9, then opening a piston for holding the solution A and dripping the solution B together, keeping the pH value of the two mixed solutions to be constant at 9, and dripping at an average rate of 2 drops per second. The liquid in the 250mL beaker was found to become increasingly turbid with a white precipitate appearing. After the solution was consumed, the resulting liquid was transferred to a three-necked flask and placed in an 80 ℃ oil bath for aging for 12h. After the completion, cooling to room temperature, suction filtering, washing with deionized water to neutrality. Drying in an oven at 60 ℃ for 12 hours. Grinding to obtain Mg 4 Al-LDH carrier.
Will be 5.08X10 -2 HAuCl in mol/L 4 0.6mL of the solution was removed, and 10mL of deionized water was added thereto and stirred, and 0.73g of urea was measured and dissolved in 20mL of deionized water, and poured into the single-necked flask. This was moved to an 80℃oil bath and stirred for 6 hours, then cooled to room temperature and 3mL of a 0.1mol/L sodium borohydride solution was added thereto for reduction for 2 hours. Filtering, and washing to neutrality. Placing in a drying oven at 60 ℃ for 8 hours. Grinding to obtain Au/Mg 4 Al-LDH catalyst. Wherein the average particle diameter of the Au particles is 12nm.
Benzyl alcohol catalytic oxidation reaction, adding 30mg of catalyst, 0.0629mol/L benzyl alcohol solution 8mL into a 25mL three-neck flask, wherein the solvent is paraxylene, continuously introducing 20mL/min of oxygen after the reaction device is installed, introducing a condensing tube for condensation reflux, starting stirring, continuously reacting for 4 hours under normal pressure, wherein the benzyl alcohol conversion rate reaches 89%, and the benzaldehyde selectivity is 92.7%.
Since the average particle diameter of the Au particles of the catalyst is 12nm, the Au particles have a larger size and a lower dispersity, which is unfavorable for benzyl alcohol catalytic oxidation, and the higher the magnesium aluminum atoms of the carrier in this example, the easier the LDH structure change, the smaller the specific surface area and the pore diameter, and the Au nanoparticles rich in defective sites are difficult to form, the catalytic activity is inferior to that of example 1.
Claims (4)
1. A gold catalyst for efficiently converting benzyl alcohol into a defect-rich site under an alkali-free condition is characterized in that a carrier in the gold catalyst is MgAl-LDH hydrotalcite; au is used as an active component of the catalyst, and is a 2D structure Au nano-sheet with the surface rich in defect sites including step sites, kinks and inflection points, and the loading amount of the Au nano-sheet is controlled to be 1.5 weight percent of the carrier; the Au active site in the catalyst is fully exposed, and the surface dispersity is as high as 40.9-43.0%.
2. The gold catalyst according to claim 1, characterized in that the average particle size of the gold active component is 3.0-3.8nm.
3. A preparation method of a gold catalyst for efficiently converting a defect-rich site of benzyl alcohol under an alkali-free condition comprises the following steps:
(1) Preparation of LDH: 0.1875mol/L of Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O mixed solution in which Mg (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The mass ratio of the O is 2:1-4:1, and the O is marked as solution A; 0.425mol/L NaOH and Na are prepared again 2 CO 3 Mixing solution, wherein, naOH and Na 2 CO 3 The mass ratio of the substances is 2.4:1, which is marked as solution B; dripping A, B solution into water at a volume ratio of 1:1 under stirring by using a coprecipitation method, keeping the pH value of the process to be 9.0, then placing the solution in an oil bath at 80 ℃ for ageing for 12 hours, cooling to room temperature, and performing suction filtration, washing and drying to obtain white LDH solid powder;
(2) Preparation of LDH-loaded Au nanoparticle catalyst:
the concentration was 5.08X10 -2 Adding 0.12mol/L urea solution into the chloroauric acid solution, wherein the mass ratio of urea to chloroauric acid substances is 400:1; after fully mixing, adding LDH solid into the mixed solution, stirring for 6 hours at 80 ℃, cooling to room temperature, adding 0.1mol/L sodium borohydride solution, wherein the mass ratio of sodium borohydride to chloroauric acid is 10:1, continuously stirring for 2 hours at room temperature, filtering after the completion, washing with deionized water until the filtrate is neutral, and drying for 8 hours in a 60 ℃ drying box.
4. The application of the gold catalyst as claimed in claim 1 or 2 in the preparation of benzaldehyde by oxidation of benzyl alcohol, characterized by the following steps:
mixing benzyl alcohol, paraxylene and a gold catalyst, wherein the mass ratio of the paraxylene to the benzyl alcohol is 100:1, and the mass ratio of the benzyl alcohol to the active component Au in the catalyst is 440:1; at 80 ℃ and normal pressure, 20mL/min of oxygen is introduced for continuous reaction for 4 hours.
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