CN116870905A - Supported monoatomic Pt catalyst and preparation method and application thereof - Google Patents
Supported monoatomic Pt catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 42
- 239000010439 graphite Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
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- 229910000510 noble metal Inorganic materials 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 14
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- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
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- 239000012266 salt solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- -1 sulfate radical Chemical class 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 11
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- 230000005855 radiation Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
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- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 230000036571 hydration Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
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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
- B01J23/38—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
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The invention relates to a supported monoatomic Pt catalyst, a preparation method and application thereof, wherein the catalyst is prepared by firstly preparing Pt 2+ Loaded to CeO 2 On the graphite oxide composite material, then the Pt is processed by microwave treatment 2+ Loaded to CeO 2 On the graphene composite carrier, finally, pt is uniformly loaded on CeO in an atomic-level form through low-temperature reduction 2 And (3) obtaining the supported monoatomic Pt catalyst on the graphene composite carrier. The preparation method provided by the invention has the characteristics of low cost, simple steps, mild conditions, better repeatability and easiness in mass production, and the prepared catalyst has the characteristics of high activity and high selectivity when being used for catalyzing phenol hydrogenation to generate cyclohexanol.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a supported monoatomic Pt catalyst, a preparation method thereof and application thereof in preparation of cyclohexanol by phenol hydrogenation.
Background
Cyclohexanol is an important chemical raw material and solvent, is mainly used for producing products such as nylon 6, nylon 66 and the like initially, and along with the rapid development of high polymer materials, cyclohexanol becomes an important raw material for synthesizing adipic acid and caprolactam in the new material field, gradually becomes an important raw material in the high polymer field, and gradually expands the application field to industries such as medicines, coatings, fuels and the like, and becomes one of indispensable raw materials. The industrial production method of cyclohexanol mainly includes cyclohexane air oxidation method, cyclohexene hydration method and phenol hydrogenation method. The phenol hydrogenation method is a cleaner technical route for producing cyclohexanol, and has the advantages of mild reaction conditions, low energy consumption, short process flow, high product purity and the like; the process utilizes phenol to completely hydrogenate to form cyclohexanol, but the product also generally contains cyclohexanone generated by partial hydrogenation of phenol. Therefore, the selection of a high activity, high selectivity catalyst is critical for the preparation of cyclohexanol by the phenol hydrogenation process.
The current catalyst for catalyzing phenol hydrogenation to generate cyclohexanol mainly comprises a platinum (Pt) noble metal catalyst. The main role is noble metal active components, and the particle size of noble metal and the choice of carrier affect the catalytic activity and selectivity of the catalyst.
The particle size of the noble metal has a great influence on the catalyst. Based on atomically dispersed metal active components, it shows great advantages in maximizing the number of active sites, enhancing selectivity to the target product, increasing the inherent catalytic activity, and reducing the amount of noble metals used.
The choice of support also has a certain influence on the catalyst. Cerium oxide is a rare earth metal oxide with advantages of cubic phase structure, good dispersibility, moderate hardness, good precision and the like, and is widely applied to various fields in industry. At the same time CeO 2 Is an alkaline substance, is favorable for the adsorption of phenol, improves the catalytic activity of the catalyst, and can be used as a catalyst carrier. However, ceria itself has a relatively small specific surface area and poor mechanical strength, and is therefore not suitable as a catalyst carrier directly. Graphene is a two-dimensional carbon material with a honeycomb structure composed of single-layer carbon atoms, and has ultrahigh specific surface area and ultrahigh specific surface areaMechanical strength is a good carrier for the catalyst. Meanwhile, the hydrophobicity of the graphene is favorable for the cyclohexanone with the hydrophobicity of a hydrogenation product to be adsorbed from the surface of the catalyst more easily, so that cyclohexanol is further generated by hydrogenation, and the selectivity of cyclohexanol is improved. The ceria is deposited on the graphene to form a composite carrier, so that the activity and selectivity of the catalyst can be improved.
At present, no literature report exists on the application of a single-atom noble metal supported cerium oxide/graphene composite carrier as a catalyst for generating cyclohexanol by phenol hydrogenation.
Disclosure of Invention
The invention aims to provide a supported monoatomic Pt catalyst and a preparation method and application thereof, and the preparation method has the advantages of low cost, simple steps, mild conditions, better repeatability and easiness for mass production, and the prepared catalyst has the active component Pt uniformly dispersed in CeO in an atomic-scale form 2 The graphene composite carrier has the characteristics of high activity and high selectivity when being used for catalyzing phenol hydrogenation to generate cyclohexanol.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a supported monoatomic Pt catalyst comprises a carrier and an active component, wherein the carrier is CeO 2 The active component is noble metal Pt which is uniformly dispersed in the CeO in an atomic form 2 And/graphene composite carrier.
Preferably, the CeO 2 CeO in graphene composite carrier 2 The content of (C) is 6-15 wt%.
Preferably, the Pt loading is 0.01 to 3wt%.
The preparation method of the supported monoatomic Pt catalyst comprises the following steps:
(1) Loading of soluble salts of Pt to CeO 2 On the graphite oxide composite material, soluble salt loading CeO of Pt is obtained 2 Graphite oxide composite material;
(2) Loading the soluble salt of Pt of step (1) with CeO 2 The graphite oxide composite material is subjected to microwave treatment to obtain PtCeO carried by soluble salt 2 A graphene composite carrier;
(3) Loading the soluble salt of Pt of the step (2) with CeO 2 And carrying out low-temperature reduction treatment on the graphene composite carrier, and carrying out suction filtration washing and drying on the obtained product to obtain the supported monoatomic Pt catalyst.
Preferably, the step (1) specifically includes the following steps: ceO is added with 2 And graphite oxide is stirred and immersed in a soluble salt solution of Pt to obtain soluble salt loaded CeO of Pt 2 Graphite oxide composite material.
Preferably, the graphite oxide in step (1) is prepared by Hummers method.
Preferably, the graphite oxide and CeO in step (1) 2 The mass ratio of (2) is 1: (0.05-0.20).
Preferably, the concentration of the soluble salt solution of Pt in the step (1) is 0.0001 to 0.015mol/L.
Preferably, the solvent of the soluble salt solution of Pt in the step (1) is water and ethanol, and the ethanol accounts for 0-100% of the volume of the solvent and does not include 0 and 100%.
Preferably, the dipping temperature in the step (1) is 20-30 ℃ and the dipping time is 1-5 h.
Preferably, the microwave treatment power in the step (2) is 700-1000W, and the microwave treatment time is 2-5 min.
Preferably, the low-temperature reduction treatment in the step (3) is reduction under a low-temperature ultraviolet light source, the reduction temperature is-50-0 ℃, the ultraviolet light source has power of 10-50W, the wavelength is 250-350 nm, and the radiation intensity is 0.05-2 mW/cm 2 The distance between the Xe ultraviolet lamp and the liquid level is 5-20 cm, and the reduction time is 1-2 h.
Preferably, the suction filtration washing in step (3) is performed under vacuum at-50 to 0 ℃.
Preferably, the drying temperature in step (3) is 20 to 70 ℃.
The invention also provides an application of the catalyst in preparing cyclohexanol by phenol hydrogenation, and under the action of the supported monoatomic hydrogenation catalyst, phenol undergoes hydrogenation reaction in a liquid phase.
Preferably, the solvent used in the hydrogenation reaction is any one or more of water, ethanol, tertiary butanol, toluene, cyclohexane and tetrahydrofuran.
Preferably, the mass ratio of the catalyst to phenol is (1-5): 1.
preferably, the hydrogenation reaction pressure is 0.1-1 MPa.
Preferably, the temperature of the hydrogenation reaction is 50-100 ℃.
Compared with the prior art, the invention has the following advantages and effects:
1. the catalyst of the invention adopts graphene and CeO 2 As a composite carrier, pt is taken as an active component, the active component is uniformly dispersed on the composite carrier in an atomic-scale form, and CeO 2 The alkalinity of the carrier is increased, which is favorable for the adsorption of phenol; ultra-high specific surface area of graphene and CeO 2 Is beneficial to the dispersion of Pt; the hydrophobicity of the graphene is beneficial to adsorbing cyclohexanone which is a product of phenol partial hydrogenation, so that cyclohexanol is further generated by hydrogenation. The catalyst of the invention has the characteristics of high activity and high selectivity when being used for catalyzing phenol hydrogenation to generate cyclohexanol.
2. The preparation method of the invention comprises the steps of Pt 2+ Loaded to CeO first 2 On the graphite oxide composite material, microwave delamination is carried out, and the large specific surface area and CeO of the graphene are utilized 2 So that Pt is 2+ Uniformly dispersing Pt among graphene layers, and finally reducing the Pt uniformly dispersed among the graphene layers by low-temperature light 2+ Reduced to atomic-scale-sized Pt, and constitutes a single-atom-structured Pt catalyst. The preparation method has the advantages of low cost, simple steps, mild conditions, good repeatability and easy mass production.
Description of the embodiments
The present invention will be described in further detail with reference to the following embodiments.
The supported monoatomic noble metal catalyst of the inventionComprises a carrier and an active component, wherein the carrier is CeO 2 The active component is noble metal Pt which is uniformly dispersed in the CeO in an atomic form 2 And/graphene composite carrier.
Preferably, the CeO 2 CeO in graphene composite carrier 2 The content of (C) is 6 to 15wt%, for example, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%.
Preferably, the platinum is supported in an amount of 0.01 to 3wt%, for example, 0.01wt%, 0.1wt%, 1wt%, 2wt%, 3wt%.
The preparation method of the supported monoatomic noble metal catalyst comprises the following steps:
(1) Loading of soluble salts of Pt to CeO 2 On the graphite oxide composite material, soluble salt loading CeO of Pt is obtained 2 Graphite oxide composite material;
(2) Loading the soluble salt of Pt of step (1) with CeO 2 The graphite oxide composite material is subjected to microwave treatment to obtain soluble salt loaded CeO of Pt 2 A graphene composite carrier;
(3) Loading the soluble salt of Pt of the step (2) with CeO 2 And carrying out low-temperature reduction treatment on the graphene composite carrier, and carrying out suction filtration washing and drying on the obtained product to obtain the supported monoatomic noble metal catalyst.
The soluble salt of Pt may be, for example, any one or a mixture of more than one of chloride, sulfate, acetate, and nitrate of Pt.
Preferably, the step (1) specifically includes the following steps: ceO is added with 2 And graphite oxide is stirred and immersed in a soluble salt solution of Pt to obtain soluble salt loaded CeO of Pt 2 Graphite oxide composite material.
Preferably, the graphite oxide in step (1) is prepared by Hummers method.
Graphite oxide is a two-dimensional carbon sheet structure of single atomic thickness having various oxygen-containing groups such as carboxyl groups at the edges of the graphite oxide sheet, epoxy groups and hydroxyl groups on the graphite oxide sheet, and the like. Common preparation methods for graphite oxide are the Brodie method, the Staudenmailer method and the Hummers method. Among them, the Hummers method has relatively good timeliness of the preparation process, and the preparation process is safer, which is the most commonly used at present. The conventional Hummers method for preparing graphene oxide can be roughly divided into three stages: (1) low temperature stage: preliminary oxidation of graphite with concentrated sulfuric acid and potassium permanganate at about 0deg.C, the graphite edges gradually oxidized to form oxygen-containing functional groups; (2) medium temperature stage: raising the temperature to about 35 ℃ to further finish the graphite oxide by the potassium permanganate; (3) high temperature stage: the temperature was raised to 98 c by an oil or water bath to dissociate the sulfur containing groups on the graphite oxide.
The Hummers method of the invention is improved based on the traditional Hummers method and specifically comprises the following steps: 15-50 mL 98wt% H 2 SO 4 Adding graphite 1g and sodium nitrate 0.5-1 g under ice bath stirring, then adding potassium permanganate 3-8 g, wherein the potassium permanganate is added in batches for a small amount, controlling the reaction temperature to be not more than 20 ℃, heating to 33-37 ℃ after uniform stirring, preferably 35 ℃, continuing stirring for 30min, slowly adding 50-100 mL of deionized water, continuing stirring for 10-30 min, adding 30wt% of hydrogen peroxide solution to reduce residual oxidant until the solution turns into bright yellow, filtering while the solution is hot, washing with 5wt% of HCl solution and deionized water until no sulfate radical in the filtrate is detected, and finally placing the filter cake in a vacuum drying box at 50-100 ℃ for full drying to obtain the graphite oxide.
Preferably, the graphite oxide and CeO in step (1) 2 The mass ratio of (2) is 1: (0.05 to 0.20), for example, 1:0.05, 1:0.1, 1:0.15, 1:0.2.
Preferably, the concentration of the soluble salt solution of Pt in the step (1) is 0.0001 to 0.015mol/L, for example, 0.0001mol/L, 0.0005mol/L, 0.001mol/L, 0.005mol/L, 0.01mol/L, 0.015mol/L.
Preferably, the solvent of the soluble salt solution of Pt in step (1) is water and ethanol, the ethanol accounts for 0-100% of the volume of the solvent and does not include 0 and 100%, and the volume ratio of the ethanol may be, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
Preferably, the impregnation temperature in the step (1) is 20 to 30 ℃, for example, 20 ℃,25 ℃,30 ℃ and the impregnation time is 1 to 5 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours and 5 hours.
Preferably, the microwave treatment power in the step (2) is 700-1000W, for example, 700W, 800W, 900W, 1000W, and the microwave treatment time is 2-5 min, for example, 2min, 3min, 4min, 5min.
Preferably, the low temperature reduction treatment in step (3) is a reduction under a low temperature uv light source having a reduction temperature of-50 to 0 ℃, for example, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, and a power of 10 to 50W, for example, 10W, 20W, 30W, 40W, 50W, a wavelength of 250 to 350nm, for example, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, and a radiation intensity of 0.05 to 2mW/cm 2 For example, it may be 0.05mW/cm 2 、0.1 mW/cm 2 、0.5 mW/cm 2 、1 mW/cm 2 、1.5 mW/cm 2 、2 mW/cm 2 The distance between the Xe ultraviolet lamp and the liquid surface is 5 to 20cm, for example, 5cm, 10cm, 15cm, 20cm, and the reduction time is 1 to 2 hours, for example, 1 hour, 2 hours.
Preferably, the suction filtration washing in step (3) is carried out under vacuum at-50 to 0 ℃, for example, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃ and 0 ℃ vacuum.
Preferably, the drying temperature in the step (3) is 20 to 70 ℃, and may be, for example, 20 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃,70 ℃.
The application of the catalyst in preparing cyclohexanol by phenol hydrogenation, wherein the specific method steps for preparing cyclohexanol by phenol hydrogenation can be referred to the prior art. Further, the solvent used in the hydrogenation reaction is any one or more of water, ethanol, tertiary butanol, toluene, cyclohexane and tetrahydrofuran.
Preferably, the mass ratio of the catalyst to phenol is (1-5): 1, for example, may be 1: 1. 2: 1. 3: 1. 4: 1. 5:1.
the hydrogenation reaction is preferably carried out at a pressure of 0.1 to 1MPa, and may be carried out at 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, or 1MPa, for example.
Preferably, the hydrogenation reaction is carried out at a temperature of 50 to 100℃and may be carried out at 50℃60℃70℃80℃90℃100 ℃.
The catalyst is used in the reaction of preparing cyclohexanol by hydrogenating phenol, and under the action of the supported monoatomic hydrogenation catalyst, phenol is subjected to hydrogenation reaction in a liquid phase, so that the catalyst has excellent catalytic activity and selectivity.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto. The experimental methods in the examples are all conventional methods unless otherwise specified; the materials used, unless otherwise specified, are all commercially available from conventional biochemical reagent manufacturers.
Example 1
46mL 98wt% H was added to a 250mL reaction flask 2 SO 4 Adding 2g of graphite powder and 1g of sodium nitrate under ice bath stirring, then adding 6g of potassium permanganate in batches, controlling the reaction temperature not to exceed 20 ℃, heating to 35 ℃ after stirring uniformly, continuing stirring for 30min, slowly adding 80mL of deionized water, continuing stirring for 20min, adding 14mL of 30wt% hydrogen peroxide solution, changing the solution into bright yellow, filtering while the solution is hot, washing with 5wt% HCl solution and deionized water until no sulfate radical is detected in the filtrate, and finally placing the filter cake in a vacuum drying oven at 60 ℃ for full drying to obtain graphite oxide.
Example 2
At 10mL of 0.0001mol/L H 2 PtCl 6 •6H 2 To an O solution (solvent is a mixture of water and ethanol in a volume ratio of 2:8) were added 1g of the graphite oxide of example 1 and 0.05g of CeO 2 Stirring at 20deg.C for 1 hr, placing into 700W microwave oven for 5min, and heating at-50deg.C with power of 10W, wavelength of 250nm, and radiation intensity of 0.05mW/cm 2 The Xe ultraviolet lamp is reduced for 2 hours, the distance between the Xe ultraviolet lamp and the liquid level is 5cm, the obtained product is filtered and washed in vacuum at the temperature of 50 ℃ below zero, and the product is dried completely at the temperature of 20 ℃ below zero, so that the supported monoatomic Pt catalyst is obtained.
Example 3
At 10mL of 0.015mol/L H 2 PtCl 6 •6H 2 To an O solution (solvent is a mixture of water and ethanol in a volume ratio of 2:8) were added 1g of graphite oxide of example 1 and 0.2g of CeO 2 Stirring at 30deg.C for 5 hr, placing in a 1000W microwave oven for 2min, and then heating at 0deg.C and power of 50W, wavelength of 350nm, and radiation intensity of 2mW/cm 2 Reducing for 1h under Xe ultraviolet lamp, vacuum filtering and washing the obtained product at 0 ℃, and drying at 70 ℃ completely to obtain the supported monoatomic Pt catalyst.
Example 4
At 10mL of 0.01mol/L H 2 PtCl 6 •6H 2 To an O solution (solvent is a mixture of water and ethanol in a volume ratio of 2:8) were added 1g of graphite oxide of example 1 and 0.1g of CeO 2 Stirring at 25deg.C for 2 hr, placing into 700W microwave oven for 5min, and heating at-40deg.C with power of 20W, wavelength of 300nm, and radiation intensity of 1mW/cm 2 The Xe ultraviolet lamp is reduced for 2 hours, the distance between the Xe ultraviolet lamp and the liquid level is 10cm, the obtained product is filtered and washed in vacuum at the temperature of minus 40 ℃, and is dried completely at the temperature of 25 ℃, so that the supported monoatomic Pt catalyst is obtained.
Comparative example 1
At 10mL of 0.01mol/L H 2 PtCl 6 •6H 2 Adding graphite oxide 1g of example 1 into O solution (mixture of water and ethanol in volume ratio of 2:8), stirring for 2 hr, placing into 700W microwave oven for 5min, and irradiating at-40deg.C and 20W power with wavelength of 300nm and radiation intensity of 1mW/cm 2 The Xe ultraviolet lamp is reduced for 2 hours, the distance between the Xe ultraviolet lamp and the liquid level is 10cm, the obtained product is filtered and washed in vacuum at the temperature of minus 40 ℃, and is dried completely at the temperature of 25 ℃, so that the supported monoatomic Pt catalyst is obtained.
Comparative example 2
1g of graphite oxide of example 1 and 0.1g of CeO were admixed 2 Placing into 700w microwave oven for 5min, and mixing with 10mL 0.01mol/L H 2 PtCl 6 •6H 2 Mixing O solution (mixture of water and ethanol at volume ratio of 2:8), stirring for 2 hr, and heating at-40deg.C and power of 20W, wavelength of 300nm, and radiation intensity of 1mW/cm 2 The Xe ultraviolet lamp is reduced for 2 hours, the distance between the Xe ultraviolet lamp and the liquid level is 10cm, the obtained product is filtered and washed in vacuum at the temperature of minus 40 ℃, and is dried completely at the temperature of 25 ℃, so that the supported monoatomic noble metal catalyst is obtained.
Comparative example 3
At 10mL of 0.01mol/L H 2 PtCl 6 •6H 2 To an O solution (solvent is a mixture of water and ethanol in a volume ratio of 2:8) were added 1g of graphite oxide of example 1 and 0.1g of CeO 2 Stirring for 2 hr, placing into 700W microwave oven for 5min, and heating at 20deg.C and power of 20W, wavelength of 300nm, and radiation intensity of 1mW/cm 2 The Xe ultraviolet lamp is reduced for 2 hours, the distance between the Xe ultraviolet lamp and the liquid level is 10cm, the obtained product is filtered and washed in vacuum at 20 ℃, and is dried completely at 25 ℃, so that the supported Pt nano catalyst is obtained.
Testing
The performance evaluation of the supported Pt nanocatalysts as described in examples 2-4 and comparative examples 1-3 was performed in a 25mL round bottom flask with a three-way valve under the following reaction conditions: 10mL of a 0.02mol/L aqueous phenol solution and 50mg of a single-atom noble metal catalyst were charged into a round-bottomed flask, the air in the round-bottomed flask was replaced 3 times with hydrogen after sealing, and after charging 0.1MPa of hydrogen into the round-bottomed flask and stirring the mixture for reaction at 50℃for 3 hours. After the reaction system was cooled to room temperature, the remaining hydrogen was discharged, and the catalyst was separated by centrifugation, and the reaction solution was subjected to GC and GC-MS analysis. The test results are shown in Table 1.
| Conversion of phenol | Selectivity of cyclohexanol | |
| Example 2 | 100% | 100% |
| Example 3 | 100% | 100% |
| Example 4 | 100% | 100% |
| Comparative example 1 | 85% | 80% |
| Comparative example 2 | 80% | 75% |
| Comparative example 3 | 70% | 70% |
The embodiment shows that the supported monoatomic Pt catalyst provided by the invention is used for the reaction of preparing cyclohexanol by phenol hydrogenation and has the characteristics of high activity and high selectivity.
The above embodiments are described in detail with respect to the technical solution of the present invention. It is obvious that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes thereto, but any changes equivalent or similar to the present invention are within the scope of the present invention.
Claims (10)
1. A supported monoatomic Pt catalyst comprises a carrier and an active component, wherein the active component is noble metal Pt, and is characterized in that the carrier is CeO 2 The noble metal Pt is uniformly dispersed in the CeO in an atomic-scale form 2 And/graphene composite carrier.
2. The supported monoatomic Pt catalyst of claim 1, wherein the CeO 2 CeO in graphene composite carrier 2 The content of (C) is 6-15 wt%.
3. The supported monoatomic Pt catalyst of claim 1, wherein the Pt loading is 0.01-3 wt%.
4. A method for preparing a supported monoatomic Pt catalyst according to any one of claims 1 to 3, characterised by comprising the steps of:
(1) Loading of soluble salts of Pt to CeO 2 On the graphite oxide composite material, soluble salt loading CeO of Pt is obtained 2 Graphite oxide composite material;
(2) Loading the soluble salt of Pt of step (1) with CeO 2 The graphite oxide composite material is subjected to microwave treatment to obtain soluble salt loaded CeO of Pt 2 A graphene composite carrier;
(3) Loading the soluble salt of Pt of the step (2) with CeO 2 And carrying out low-temperature reduction treatment on the graphene composite carrier, and carrying out suction filtration washing and drying on the obtained product to obtain the supported monoatomic Pt catalyst.
5. The method according to claim 4, wherein the step (1) comprises the steps of: ceO is added with 2 And graphite oxide is stirred and immersed in a soluble salt solution of Pt to obtain soluble salt loaded CeO of Pt 2 Graphite oxide composite material.
6. The method according to claim 4 or 5, wherein the graphite oxide in step (1) is prepared by a Hummers method, the graphite oxide and CeO 2 The mass ratio of (2) is 1: (0.05-0.20); the Hummers method comprises the following steps: adding graphite and sodium nitrate into sulfuric acid under ice bath stirring, then adding potassium permanganate in batches, controlling the reaction temperature not to exceed 20 ℃, heating to 33-37 ℃ after stirring uniformly, then slowly adding deionized water, adding hydrogen peroxide solution to reduce residual oxidant until the solution turns bright yellow, filtering, washing with HCl solution and deionized water until sulfate radical is not contained in the filtrate, and finally fully drying the filter cake to obtain the graphite oxide.
7. The method according to claim 4, wherein the microwave treatment power in the step (2) is 700 to 1000W and the microwave treatment time is 2 to 5min.
8. The method according to claim 4, wherein the low-temperature reduction treatment in the step (3) is reduction under a low-temperature ultraviolet light source, and the reduction temperature is-50 to 0 ℃.
9. The process according to claim 4, wherein the suction filtration washing in step (3) is performed under vacuum at-50 to 0℃and the drying temperature is 20 to 70 ℃.
10. Use of a supported monoatomic Pt catalyst according to any one of claims 1 to 3 for the preparation of cyclohexanol by hydrogenation of phenol.
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