CN117085677A - Method for synthesizing MOF derivative composite catalytic material by in-situ reduction and calcination - Google Patents
Method for synthesizing MOF derivative composite catalytic material by in-situ reduction and calcination Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001354 calcination Methods 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 230000009467 reduction Effects 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 38
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- 239000002243 precursor Substances 0.000 claims abstract description 16
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- 238000010438 heat treatment Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 10
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 230000002829 reductive effect Effects 0.000 claims description 5
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002904 solvent Substances 0.000 description 11
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
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- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000619 electron energy-loss spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013183 functionalized metal-organic framework Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- 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
- B01J23/892—Nickel and noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
- B01J37/343—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 ultrasonic wave energy
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Abstract
A method for synthesizing a MOF derivative composite catalytic material by in-situ reduction and calcination, wherein the composite catalytic material has strong interaction between metal and carrier, and belongs to the field of catalyst materials. Firstly, hydrothermally synthesizing a precursor MOF (metal organic framework) by corresponding transition metal elements and organic ligands in a proper solution, then, according to the structural characteristics of materials, firstly reacting amino groups in the amino-functional MOF with formaldehyde to form reducing groups, and encapsulating noble metal clusters by a simple in-situ reduction method, wherein the obtained mixture has uniformly dispersed noble metal clusters. Then the noble metal clusters/oxide composite material with SMS I effect is converted in inert atmosphere, and finally the obtained composite catalytic material has stable structure, regular appearance, uniform dispersion of noble metal clusters, good thermal stability and excellent electrocatalytic performance. The invention has low preparation cost and simple synthesis process, and is suitable for large-scale mass production.
Description
Technical Field
The invention belongs to the field of catalyst materials, relates to a preparation method of a novel catalytic material, and in particular relates to a preparation method of an MOF (metal organic framework) -derived composite catalytic material synthesized by in-situ reduction and calcination and having a strong metal-carrier interaction (SMSI) effect.
Background
In the field of electrocatalysis, high activity and high selectivity electrocatalysts are a prerequisite. Noble metals and their alloys (e.g., pd-Au, pt-Hg and Pd-Hg) are currently the most effective catalysts with small overpotential and high selectivity. However, the scarcity of noble metals prevents their large scale application. The noble metal is loaded/encapsulated on the reducible oxide carrier, the reducible carrier and the metal have strong interaction, and the carrier transmits partial electrons to the metal, namely, the metal-carrier strong interaction (SMSI) effect, so that the method is an effective strategy for improving the dispersity of the noble metal, modifying the electrons and the geometric structure, obtaining high active surface area, adjusting adsorption energy and promoting electron transfer. It was found for the first time from Tauster et al in 1978 that traditionally this effect was achieved by subjecting a reducible metal oxide support (e.g.TiO 2 、Ta 2 O 5 And Nb (Nb) 2 O 5 ) The carrier is loaded with noble metal nano-particles (such as Pd, ru, au, ir, os and Rh) by high temperature annealing. [1] The supported metal is encapsulated by migration of the reduced metal oxide support to the noble metal NPs surface, thereby minimizing surface energy. The interaction between the coating layer and the noble metal NPs regulates the activity and the selectivity of the supported noble metal catalyst, and greatly improves the catalytic stability. In addition to the traditional way of calcination synthesis in reducing atmosphere, many new methods are developed. Most catalysts with SMSI effect precious gold on oxide by impregnation or photo-depositionIs loaded and then calcined in a reducing atmosphere, e.g. Xiao F.S. etc [2] NaBH at 0 ℃ 4 The Au nano particles are reduced by aqueous solution, then anatase is added, and the Au/TiO is obtained by loading by a sol immobilization method 2 The method has higher requirements on experimental operation, and the particle size distribution of the particles obtained by the chemical reduction method is wider, so that the large-scale application of the particles is limited; van Bokhoven, J.A. et al [3] The P25 is used for loading platinum (II) by an immersion method, and then the material is treated under the atmosphere of rare gas He to obtain a product, so that the cost is high; wu z.l. et al [4] Pd/TiO by deposition-urea precipitation (DPU) using anatase titanium dioxide and palladium chloride as starting materials 2 Most of these methods use commercial titanium oxide as a raw material, and the noble metal loading is limited to the surface. Therefore, the search for suitable carriers is key to uniformly and efficiently distribute metal Nanoparticles (NPs) in electrocatalysts and to protect the dispersed sites from migration and aggregation.
The Metal Organic Framework (MOFs) material is formed by flexibly combining various organic ligands and coordination metal nodes, so that the noble metal NPs are well dispersed and ultra-low loaded in a pore structure of an adjustable chemical environment. [5] Therefore, the metal nanoparticles, clusters or single atoms carried by the MOFs derivatives are widely demonstrated to have excellent catalytic properties thanks to the synergistic effect between the MOFs derivatives and the metal, providing the possibility of achieving a strong metal-support interaction (SMSI), inheriting the characteristics of the porous structure and the high activity of the metal sites of the MOFs. [6]
[1]Tauster S J,Fung S C,Baker R T,et al.Strong Interactions in Supported-Metal Catalysts[J].Science,1981,211(4487):1121-1125.
[2]Zhang J,Wang H,Wang L,et al.Wet-Chemistry Strong Metal-Support Interactions in Titania-Supported Au Catalysts[J].Journal of the American Chemical Society,2019,141(7):2975-2983.
[3]Beck A,Huang X,Artiglia L,et al.The Dynamics of Overlayer Formation on Catalyst Nanoparticles and Strong Metal-Support Interaction[J].Nature Communication,2020,11(1):3220.
[4]Polo-Garzon F,Blum T F,Bao Z H,et al.In Situ Strong Metal–Support Interaction(SMSI)Affects Catalytic Alcohol Conversion[J].ACS Catalysis,2021,11(4):1938-1945.
[5]Beck A,Huang X,Artiglia L,et al.The Dynamics of Overlayer Formation on Catalyst Nanoparticles and Strong Metal-Support Interaction[J].Nature Communication,2020,11(1):3220.
[6]Dutta S,Lee I S.Metal–Organic Framework based Catalytic Nanoreactors:Synthetic Challenges and Applications[J].Materials Chemistry Frontiers,2021,5(11):3986-4021.
Disclosure of Invention
The invention aims to provide a method for synthesizing an MOF derivative composite catalytic material with metal-carrier strong interaction by in-situ reduction and calcination and a preparation method thereof, so that the method is widely applied to scientific research and industrial production.
According to the invention, the characteristic of a metal organic framework compound is utilized, amino-functionalized MOF is selected as a precursor for material synthesis, and a very simple normal-temperature and normal-pressure double-solvent method is adopted to treat the precursor with aldehyde substances and then reduce metal clusters in situ. The noble metal particles are successfully loaded on MOFs through an in-situ reduction method, so that the noble metal particles are uniform in size and ultralow in loading capacity, are tightly combined with a carrier and have strong synergistic effect, and are then converted into noble metal clusters/oxides with SMSI effect under an inert atmosphere. In the synthesis process, only a hydrothermal box and a tube furnace are used, no complex professional instrument is used, and the process is simple and continuous. The prepared catalyst has rich active sites, high utilization rate of the loaded metal atoms and excellent catalytic performance potential. When the reaction of generating hydrogen peroxide by di-electron oxygen reduction and electrocatalysis is used as a probe reaction, the performance of the catalyst synthesized by the process exceeds that of most catalysts already reported.
The invention provides a method for synthesizing a MOF derivative composite catalytic material through in-situ reduction and calcination, wherein the MOF derivative composite catalytic material has strong metal-carrier interaction, and comprises the following steps of:
(1) Selecting proper metal salt solution and organic ligand, respectively dissolving in deionized water or organic solvent, adjusting pH value according to different metal salt solutions, mixing with ultrasound, dispersing uniformly, and performing hydrothermal crystallization;
(2) The product after hydrothermal crystallization is fully washed and centrifugally dried to obtain a precursor MOF;
(3) Dissolving a certain amount of precursor MOF powder in an aqueous solution containing alcohols and aldehydes, stirring by ultrasonic, dispersing uniformly, and carrying out water bath treatment;
(4) The product after water bath treatment is fully washed, centrifuged and dried in vacuum to obtain a reducing precursor MOF;
(5) Dissolving a certain amount of reducing precursor MOF powder in alkane-containing solution, adding a proper amount of noble metal aqueous solution for in-situ reduction, uniformly stirring, and carrying out water bath heating treatment;
(6) Separating out supernatant, and vacuum drying to obtain a noble metal-loaded MOF precursor;
(7) And carrying out heat treatment on the obtained MOF precursor loaded with the noble metal in a tube furnace, wherein the atmosphere is inert gas, and obtaining the MOF derivative composite catalytic material with the metal-carrier strong interaction.
Wherein the metal salt solution is one of titanium salt, nickel salt, ferric salt and copper salt; the organic ligand is one of 2-amino terephthalic acid, 2, 5-diamino terephthalic acid, 2-aminobenzoic acid, p-aminobenzoic acid and phenylalanine; the organic solvent is one of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide and N, N-diethylacetamide and methanol; the alcohol substances are propylene glycol, ethanol, methanol and the like, the aldehyde substances are formaldehyde, and the volume ratio of the aldehyde substances to deionized water is controlled at 1:4:5 to 1:4:8, 8; the alkane substance is n-hexane, n-heptane and the like; the noble metal source is one or more of chloroauric acid, palladium chloride and ammonium chloroplatinate, and various noble metal sources can be directly used or can be used in a solution form, preferably can be used in a solution form, and the concentration of the noble metal aqueous solution can be 0.1-10mmol/L; the inert gas is one of argon and nitrogen.
Further, in the step (1), the titanium salt, the nickel salt, the iron salt and the copper salt are mixed uniformly with the 2-amino terephthalic acid, the 2, 5-diamino terephthalic acid, the 2-amino benzoic acid, the p-amino benzoic acid and the phenylalanine according to the adding amount of the 2-amino terephthalic acid, the 2-amino benzoic acid, the p-amino benzoic acid and the phenylalanine in a molar ratio of 1:8 to 1:2, the mixing temperature is 15-35 ℃, the ultrasonic time is 5-60 minutes, and the pH of the stirring solution is 1-12 according to the difference of metal salt solutions.
Further, in step (1), the crystallization is performed in a crystallization kettle well known in the art. The crystallization conditions may be various conditions commonly used in the art, but preferably, the crystallization conditions include a crystallization temperature of 120 to 180℃and a crystallization time of 2 to 10 hours.
Further, in the step (1), the stirring conditions are not particularly limited as long as the obtained mixed solution is ensured to be a uniform clear transparent solution, but preferably, the stirring conditions include ultrasonic stirring at 15 to 30 ℃ for 5 to 60 minutes; more preferably, the stirring temperature is 20-25℃and the stirring time is 10-30 minutes.
Further, in the step (2), the centrifugal rotation speed is 6000-10000 revolutions per minute, and the centrifugal time is 5-40 minutes; the washing process is that the used organic solution and deionized water are alternately washed for 2-5 times; the drying temperature is 50-80 ℃ and the drying time is 6-24 hours.
Further, in step (3), the water bath heating treatment is performed in a beaker well known in the art. The water bath heating conditions may be various conditions commonly used in the art, but preferably, the water bath heating conditions include a water bath temperature of 20 to 60℃and a crystallization time of 1 to 10 hours.
Further, in the step (4), the centrifugal rotation speed is 6000-10000 revolutions per minute, and the centrifugal time is 5-40 minutes; the washing process is that absolute ethyl alcohol and deionized water are alternately washed for 2-5 times; the drying temperature is 60-90 ℃ and the drying time is 6-24 hours.
Further, in the step (5), the addition amount of the noble metal aqueous solution is very important, and in general, the mass ratio of the noble metal aqueous solution to the addition amount of the obtained powder is 1:1000 to 1:50; preferably, the mass ratio of the noble metal aqueous solution to the added amount of the obtained powder is 1:500 to 1:100.
Further, in step (5), the water bath heating treatment is performed in a beaker well known in the art. The water bath heating conditions may be various conditions commonly used in the art, but preferably, the water bath heating conditions include a water bath temperature of 20 to 60℃and a crystallization time of 1 to 5 hours.
Further, in the step (6), the drying temperature is 50-90 ℃ and the drying time is 6-24 hours.
Further, in the step (7), the temperature rising rate is 0.5-10 ℃/min, the temperature is raised to 450-850 ℃, and the temperature is kept for 1-5h.
The invention adopts very simple solvothermal and double-solvent synthesis modes, and has simple and efficient process. Firstly, hydrothermally synthesizing a precursor MOF (metal organic framework) by corresponding transition metal elements and organic ligands in a proper solution, then, according to the structural characteristics of materials, firstly reacting amino groups in the amino-functional MOF with formaldehyde to form reducing groups, and encapsulating noble metal clusters by a simple in-situ reduction method, wherein the obtained mixture has uniformly dispersed noble metal clusters. Then the noble metal cluster/oxide composite material with SMSI effect is converted in inert atmosphere, and finally the obtained material has stable structure and excellent electrocatalytic performance.
In the material synthesis process, the process is safe and efficient (only water bath heating and stirring and hydrothermal crystallization are performed, and low-temperature and other complex environments are not involved), the instrument is simple (the main instrument for solvothermal synthesis is a beaker and a centrifuge, and the main instrument for calcination is a tube furnace), the cost is effectively controlled (the atmosphere of the tube furnace is only nitrogen or argon, and helium and other expensive gases are not involved), and the process continuity is strong.
The MOF derivative composite catalytic material synthesized by in-situ reduction and calcination and having the strong interaction of metal and carrier has the advantages of stable structure, regular appearance, uniform dispersion of noble metal clusters and good thermal stability. Therefore, the synthetic method is expected to be widely applied to the research and production of novel catalyst materials. The invention has low preparation cost and simple synthesis process, and is suitable for large-scale mass production. Therefore, it has wider scientific research and practical value.
Drawings
FIG. 1 is Au/TiO 2 A (a) scanning electron microscope image, (b) high resolution transmission electron microscope image and (c) a corresponding electron energy loss spectrum of the marked region of the material.
FIG. 2 is Pd/TiO 2 Scanning electron microscopy and high resolution transmission electron microscopy of materials.
FIG. 3 is a scanning electron microscope image of Au/NiO material.
FIG. 4 is a scanning electron microscope image of Pd/NiO material.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples. Those skilled in the art will understand that the following examples are only preferred embodiments of the present invention in order to better understand the present invention, and thus should not be construed as limiting the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art, and it is intended to cover all such modifications, equivalents, and alternatives falling within the spirit and principles of this invention. The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used, unless specified, are all purchased from conventional biochemical reagent manufacturers.
In the following examples, a bench top high-speed centrifuge (Xiangyi H-1650) was used for centrifugation; the transmission electron microscope photograph is obtained by adopting a lanthanum hexaboride transmission electron microscope (Tecnai G2 20S-TWIN); scanning electron micrographs were obtained using a field emission scanning electron microscope (ZEISS suprimt 55).
Embodiment one:
weighing 2.72g of 2-amino terephthalic acid (15 mmol) and 1.28mL of tetra-N-butyl titanate (3.75 mmol) at 25 ℃ to be dissolved in 45mL of N, N-Dimethylformamide (DMF) and 5mL of absolute methanol, putting into an ultrasonic machine for ultrasonic treatment, mixing and stirring until the materials are completely dissolved, transferring the materials into a crystallization kettle, crystallizing at 180 ℃ for 16h, centrifuging and drying for 24h after crystallization is finished to obtain MIL-125-NH 2 A material; to be also provided withIntroduction of primordial groups into MIL-125-NH 2 In the organic framework of (2), 1g of MIL-125-NH 2 Adding into 50ml of formaldehyde-ethanol-water (5:20:25, v/v/v) mixture, stirring at 40deg.C for 120min, centrifuging, washing, vacuum drying at 80deg.C for 12 hr, and named MIL-125-NH-CH 2 OH. In the double solvent method, n-hexane is used as a hydrophobic solvent, and 0.2g of MIL-125-NH-CH is stirred continuously 2 OH was uniformly dispersed in 20mL of anhydrous n-hexane, and a certain amount of NH was added dropwise to the solution 4 AuCl 4 Aqueous solution, control Au + Content and MIL-125-NH-CH 2 The mass ratio of OH is 1:100, stirring the mixture at 40deg.C for 2 hr, decanting the supernatant, and drying at 60deg.C for 12 hr to obtain Au/MIL-125-NH-CH 2 OH. Calcining in a tube furnace under argon gas at a heating rate of 0.5-1deg.C/min, heating to 500-550deg.C, and maintaining for 2-2.5 hr to obtain Au/TiO 2 A material.
Embodiment two:
weighing 2.72g of 2-amino terephthalic acid (15 mmol) and 1.28mL of tetra-N-butyl titanate (3.75 mmol) at 25 ℃ to be dissolved in 45mL of N, N-Dimethylformamide (DMF) and 5mL of absolute methanol, putting into an ultrasonic machine for ultrasonic treatment, mixing and stirring until the materials are completely dissolved, transferring the materials into a crystallization kettle, crystallizing at 180 ℃ for 16h, centrifuging and drying for 24h after crystallization is finished to obtain MIL-125-NH 2 A material; to introduce reducing groups into MIL-125-NH 2 In the organic framework of (2), 1g of MIL-125-NH 2 Adding into 50ml of formaldehyde-ethanol-water (5:20:25, v/v/v) mixture, stirring at 40deg.C for 120min, centrifuging, washing, vacuum drying at 80deg.C for 12 hr, and named MIL-125-NH-CH 2 OH. In the double solvent method, n-hexane is used as a hydrophobic solvent, and 0.2g of MIL-125-NH-CH is stirred continuously 2 OH was uniformly dispersed in 20mL of anhydrous n-hexane, and a certain amount of (NH) was added dropwise to the solution 4 ) 2 PdCl 4 Aqueous solution, control Pd 2+ Content and MIL-125-NH-CH 2 The mass ratio of OH is 1:100, stirring the mixture at 40deg.C for 2 hr, decanting the supernatant, and vacuum drying at 60deg.C for 12 hr to obtain Pd/MIL-125-NH-CH 2 OH. Calcining in a tube furnace under argon gas at a heating rate of 0.5-1deg.C/min, heating to 500-550deg.C, and maintaining the temperature for 2-2.5h, finally obtaining Pd/TiO 2 A material.
Embodiment III:
weighing 18.13mg of 2-amino terephthalic acid (0.1 mmol) and 49.6mg of nickel acetate tetrahydrate (0.2 mmol) at 25 ℃ respectively dissolving in 12mL of N, N-Dimethylacetamide (DMAC) and 12mL of deionized water, putting into an ultrasonic machine for ultrasonic treatment, mixing and stirring until all the materials are dissolved, transferring to a crystallization kettle, crystallizing at 150 ℃ for 3h, centrifuging and drying for 24h after crystallization is finished to obtain Ni-MOF-NH 2 A material; to introduce a reducing group into Ni-MOF-NH 2 In the organic framework of (2), 1g of Ni-MOF-NH 2 Adding into 50ml of formaldehyde-ethanol-water (5:20:25, v/v/v) mixture, stirring at 40deg.C for 120min, centrifuging, washing, vacuum drying at 80deg.C for 12 hr, and named Ni-MOF-NH-CH 2 OH. In the double solvent method, 0.2g of Ni-MOF-NH-CH is stirred continuously by using n-hexane as a hydrophobic solvent 2 OH was uniformly dispersed in 20mL of anhydrous n-hexane, and a certain amount of NH was added dropwise to the solution 4 AuCl 4 Aqueous solution, control Au + Content and Ni-MOF-NH-CH 2 The mass ratio of OH is 1:100, after stirring the mixture at 40℃for 2 hours, decanting the supernatant and vacuum drying at 60℃for 12 hours to give Au/Ni-MOF-NH-CH 2 OH. And then calcining in a tube furnace, wherein the calcining atmosphere is argon, the heating rate is 4-5 ℃/min, the temperature is increased to 750-800 ℃, and the temperature is kept for 2-2.5h, so that the Au/NiO material is finally obtained.
Embodiment four:
weighing 18.13mg of 2-amino terephthalic acid (0.1 mmol) and 49.6mg of nickel acetate tetrahydrate (0.2 mmol) at 25 ℃ respectively dissolving in 12mL of N, N-Dimethylacetamide (DMAC) and 12mL of deionized water, putting into an ultrasonic machine for ultrasonic treatment, mixing and stirring until all the materials are dissolved, transferring to a crystallization kettle, crystallizing at 150 ℃ for 3h, centrifuging and drying for 24h after crystallization is finished to obtain Ni-MOF-NH 2 A material; to introduce a reducing group into Ni-MOF-NH 2 In the organic framework of (2), 1g of Ni-MOF-NH 2 Adding into 50ml of formaldehyde-ethanol-water (5:20:25, v/v/v) mixture, stirring at 40deg.C for 120min, centrifuging, washing, vacuum drying at 80deg.C for 12 hr, and named Ni-MOF-NH-CH 2 OH. In the two-solvent method, 0.2g of Ni-in-one was stirred continuously using n-hexane as a hydrophobic solventMOF-NH-CH 2 OH was uniformly dispersed in 20mL of anhydrous n-hexane, and a certain amount of (NH) was added dropwise to the solution 4 ) 2 PdCl 4 Aqueous solution, control Pd 2+ Content and Ni-MOF-NH-CH 2 The mass ratio of OH is 1:100, stirring the mixture at 40deg.C for 2h, decanting the supernatant, and vacuum drying at 60deg.C for 12h to obtain Pd/Ni-MOF-NH-CH 2 OH. And then calcining in a tube furnace, wherein the calcining atmosphere is argon, the heating rate is 4-5 ℃/min, the temperature is increased to 750-800 ℃, and the temperature is kept for 2-2.5h, so that the Pd/NiO material is finally obtained.
Fifth embodiment:
weighing 18.13mg of 2-amino terephthalic acid (0.1 mmol) and 16.68mg of ferric sulfate heptahydrate (0.06 mmol) at 25 ℃ respectively dissolving in 12mL of N, N-Dimethylacetamide (DMAC) and 12mL of deionized water, putting into an ultrasonic machine for ultrasonic treatment, mixing and stirring until all the materials are dissolved, transferring to a crystallization kettle, crystallizing at 150 ℃ for 3h, centrifuging and drying for 24h after crystallization is finished to obtain Fe-MOF-NH 2 A material; to introduce reducing groups into Fe-MOF-NH 2 In the organic framework of (2), 1g of Fe-MOF-NH 2 Adding into 50ml of formaldehyde-ethanol-water (5:20:25, v/v/v) mixture, stirring at 40deg.C for 120min, centrifuging, washing, vacuum drying at 80deg.C for 12 hr, and named Fe-MOF-NH-CH 2 OH. In the double solvent method, 0.2g of Fe-MOF-NH-CH is stirred continuously by using n-hexane as a hydrophobic solvent 2 OH was uniformly dispersed in 20mL of anhydrous n-hexane, and a certain amount of (NH) was added dropwise to the solution 4 ) 2 PtCl 6 Control of Pt in aqueous solution 4+ Content and Fe-MOF-NH-CH 2 The mass ratio of OH is 1:100, stirring the mixture at 40deg.C for 2h, decanting the supernatant, and vacuum drying at 60deg.C for 12h to obtain Pt/Fe-MOF-NH-CH 2 OH. Calcining in a tube furnace under argon gas at a heating rate of 4-5deg.C/min, heating to 750-800deg.C, and maintaining for 2-2.5 hr to obtain Pt/FeO x A material.
The present invention will be described with reference to the above examples, but the present invention is not limited to the above-described detailed features and detailed methods, and it is not intended that the present invention be limited to the above-described detailed features and detailed methods. It will be apparent to those skilled in the art that any modifications, equivalent substitutions for selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., as well as other variations made within the knowledge of one of ordinary skill in the art without departing from the spirit of the invention, are intended to fall within the scope of the invention and the scope of the disclosure.
Claims (10)
1. A method of in situ reduction calcination synthesis of a MOF-derived composite catalytic material having a metal-support strong interaction, comprising the steps of:
(1) Selecting proper metal salt solution and organic ligand, respectively dissolving in deionized water or organic solvent, adjusting pH value according to different metal salt solutions, mixing with ultrasound, dispersing uniformly, and performing hydrothermal crystallization;
(2) The product after hydrothermal crystallization is fully washed and centrifugally dried to obtain a precursor MOF;
(3) Dissolving a certain amount of precursor MOF powder in an aqueous solution containing alcohols and aldehydes, stirring by ultrasonic, dispersing uniformly, and carrying out water bath treatment;
(4) The product after the hydrothermal treatment is fully washed, centrifuged and dried in vacuum to obtain a reducing precursor MOF;
(5) Dissolving a certain amount of reducing precursor MOF powder in alkane-containing solution, adding a proper amount of noble metal aqueous solution for in-situ reduction, uniformly stirring, and carrying out water bath heating treatment;
(6) Separating out supernatant, and vacuum drying to obtain a noble metal-loaded MOF precursor;
(7) And carrying out heat treatment on the obtained MOF precursor loaded with the noble metal in a tube furnace, wherein the atmosphere is inert gas, and obtaining the MOF derivative composite catalytic material with the metal-carrier strong interaction.
2. The method for synthesizing the MOF derivative composite catalytic material by in-situ reduction and calcination according to claim 1, wherein the metal salt solution is one of titanium salt, nickel salt, iron salt and copper salt; the organic ligand is one of 2-amino terephthalic acid, 2, 5-diamino terephthalic acid, 2-aminobenzoic acid, p-aminobenzoic acid and phenylalanine; the organic solvent is one of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide and N, N-diethylacetamide and methanol; the alcohol substances are propylene glycol, ethanol and methanol; the aldehyde substance is formaldehyde; the volume ratio of aldehyde substances, alcohol substances and deionized water is controlled at 1:4:5 to 1:4:8, 8; the alkane substance is n-hexane and n-heptane; the noble metal source is one or more of chloroauric acid, palladium chloride acid and ammonium chloroplatinate, and various noble metal sources can be directly used or used in the form of solution; when the noble metal is used in the form of a solution, the concentration of the noble metal aqueous solution is 0.1-10mmol/L; the inert gas is one of argon and nitrogen.
3. The method for synthesizing the MOF-derived composite catalytic material by in-situ reduction and calcination according to claim 1, wherein in the step (1), the molar ratio of the titanium salt, the nickel salt, the iron salt and the copper salt to the addition amount of the 2-amino terephthalic acid, the 2, 5-diamino terephthalic acid, the 2-amino benzoic acid, the p-amino benzoic acid and the phenylalanine is 1:8 to 1:2, the mixing temperature is 15-35 ℃, the ultrasonic time is 5-60 minutes, and the pH of the stirring solution is 1-12 according to the metal salt solution.
4. The method of in situ reductive calcination to synthesize a MOF-derived composite catalyst material according to claim 1, wherein in step (1), the crystallization is performed in a crystallization kettle well known in the art; the crystallization conditions include a crystallization temperature of 120-180 ℃ and a crystallization time of 2-10 hours.
5. The method of in situ reductive calcination to synthesize MOF-derived composite catalyst material according to claim 1, wherein in step (1), the temperature of ultrasonic agitation is 15 to 30 ℃ and the agitation time is 5 to 60 minutes.
6. The method for synthesizing the MOF-derived composite catalytic material by in-situ reduction and calcination according to claim 1, wherein in the step (2), the centrifugation speed is 6000-10000 revolutions per minute and the centrifugation time is 5-40 minutes; the washing process is that the used organic solution and deionized water are alternately washed for 2-5 times; the drying temperature is 50-80 ℃ and the drying time is 6-24 hours.
7. The method of in situ reduction calcination synthesis of MOF derived composite catalytic material according to claim 1, wherein in step (3), the water bath temperature is 20-60 ℃ and crystallization time is 1-10 hours.
8. The method for synthesizing the MOF-derived composite catalytic material by in-situ reduction and calcination according to claim 1, wherein in the step (4), the centrifugation speed is 6000-10000 revolutions per minute and the centrifugation time is 5-40 minutes; the washing process is that absolute ethyl alcohol and deionized water are alternately washed for 2-5 times; the drying temperature is 60-90 ℃ and the drying time is 6-24 hours.
9. The method of in situ reductive calcination synthesis of MOF-derived composite catalytic material according to claim 1, wherein in step (5), the mass ratio of the noble metal aqueous solution to the amount of the resulting powder added is from 1:1000 to 1:50.
10. The method for synthesizing the MOF derivative composite catalytic material by in-situ reduction and calcination according to claim 1, wherein in the step (5), the water bath heating condition comprises a water bath temperature of 20-60 ℃ and a crystallization time of 1-5 hours;
in the step (6), the drying temperature is 50-90 ℃ and the drying time is 6-24 hours; in the step (7), the temperature rising rate is 0.5-10 ℃/min, the temperature is raised to 450-850 ℃, and the temperature is kept for 1-5h.
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