CN112642487B - UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof - Google Patents
UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof Download PDFInfo
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- CN112642487B CN112642487B CN202011432771.XA CN202011432771A CN112642487B CN 112642487 B CN112642487 B CN 112642487B CN 202011432771 A CN202011432771 A CN 202011432771A CN 112642487 B CN112642487 B CN 112642487B
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- 239000013208 UiO-67 Substances 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 37
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 52
- 229910021118 PdCo Inorganic materials 0.000 claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 40
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 14
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
- 150000003754 zirconium Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 7
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012876 carrier material Substances 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000001914 filtration Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000013766 direct food additive Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/23—
-
- B01J35/394—
-
- B01J35/397—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
The invention discloses a UiO-67 encapsulated metal nanoparticle catalyst and a preparation method and application thereof. Such UiO-67 encapsulated metal nanoparticle catalysts comprise a support and an active component; wherein the carrier is a metal organic framework material UiO-67, and the active component is PdCo alloy nano particles; the PdCo alloy nanoparticles are encapsulated in the inner cavity of UiO-67. In the UiO-67 encapsulated metal nanoparticle catalyst prepared by the invention, the PdCo alloy nanoparticles are encapsulated in the inner cavity of the UiO-67, the particle size of the PdCo alloy nanoparticles is uniform and highly dispersed, the PdCo alloy nanoparticles have very high activity, and the PdCo alloy nanoparticles are applied to the catalytic oxidation reaction of acetaldehyde and show excellent catalytic performance.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a UiO-67 encapsulated metal nanoparticle catalyst and a preparation method and application thereof.
Background
With the continuous improvement of the living standard of people and the rapid development of the automobile industry, automobiles have moved into the daily life of common people, and the problems of air quality pollution in automobiles, which are directly related to physical and psychological health, are increasingly focused due to the continuous improvement of environmental protection consciousness and self-protection consciousness of people. It has been recognized that in-car air pollution has become a stealth killer, with Volatile Organic Compounds (VOCs) being the most significant pollution, severely compromising human health.
At present, the management and control of the VOCs in the whole car is mainly realized by developing and using green environment-friendly materials, so that the direct addition amount of the materials used in the car and the object substances in the parts is reduced, and the release amount of the VOCs in the whole car is further reduced. However, acetaldehyde is not a direct additive in materials and parts, but is generated by decomposition of other substances in the using process, is greatly influenced by seasons and environment, is also an easily overstocked substance of the whole automobile, and the generation mechanism and influencing factors are hot spots for research and control difficulties in the automobile industry. Among eight substances controlled by VOCs in the vehicle specified in national standard GB/T27630-2011, acetaldehyde is the most difficult to control, and the overall average value in the industry is 0.078mg/m 3 Severely exceeding the prescribed limit of 0.050mg/m 3 . The acetaldehyde content of main interior parts such as seats, door guard plates, ceilings, carpets, front walls, instrument panels, auxiliary instrument panels, spare tire cover plates and the like in the automobile is the main cause of exceeding the standard of the acetaldehyde content of the whole automobile.
Acetaldehyde is a gas pollutant with irritation, and long-term inhalation of acetaldehyde gas can cause symptoms such as headache, nausea, immunity reduction, allergy and the like, and serious malformation, cancer and the like. Therefore, research on technical means for effectively degrading acetaldehyde gas is particularly important. At present, the treatment of acetaldehyde mainly comprises methods of adsorption of adsorbent, photocatalysis of photocatalyst, removal of acetaldehyde by thermocatalytic oxidation, and the like. For the adsorption method, the adsorption method is invalid when the adsorbents such as active carbon/molecular sieve reach adsorption saturation, and if the adsorbents are not replaced in time, the secondary pollution is possibly caused by desorption of acetaldehyde. The photocatalytic method adopts photocatalyst (TiO 2 ) The acetaldehyde is degraded, but an external ultraviolet light source is usually needed, so that the degradation efficiency under visible light is low, and the wide application of the acetaldehyde is limited. While the thermocatalytic oxidation process can completely oxidize acetaldehyde into CO 2 And H 2 O, will not produce secondary pollution, is the most thorough method for removing acetaldehyde, has important practical application value. But is currently developedThe single catalyst has unsatisfactory adsorptivity, cannot be enriched on the surface and has low catalytic efficiency; in most cases, the temperature at which acetaldehyde is completely converted is high, in some cases even above 200 ℃. These problems become the elbows for the development of catalytic purification materials, and there is a need to improve the preparation method and process, prepare porous materials and the like to increase the specific surface area of the catalyst, or prepare composite catalysts by doping, loading, modification and the like to improve the catalytic efficiency on acetaldehyde.
Disclosure of Invention
In order to solve the problems of the prior acetaldehyde catalytic purification material, the invention aims to provide a UiO-67 encapsulated metal nanoparticle catalyst PdCo@UiO-67, and the second aim of the invention is to provide a preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, and the third aim of the invention is to provide an application of the UiO-67 encapsulated metal nanoparticle catalyst in an acetaldehyde catalytic oxidation reaction.
The inventive concept of the present invention is as follows: the nano-particle catalyst of the UiO-67 encapsulated PdCO alloy is prepared by preparing a metal organic framework material UiO-67 by adopting a zirconium salt and an organic ligand containing a bipyridine unit through a solvothermal method, then coupling and coordinating the bipyridine unit with Pd salt and Co salt, and then performing heat treatment in a reducing atmosphere.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a UiO-67 encapsulated metal nanoparticle catalyst, which comprises a carrier and an active component, wherein the carrier is a metal nanoparticle catalyst; wherein the carrier is a metal organic framework material UiO-67, and the active component is PdCo alloy nano particles; the PdCo alloy nanoparticles are confined within the inner cavity of the UiO-67 framework.
Preferably, in the UiO-67 encapsulated metal nanoparticle catalyst, the loading amount of the PdCO alloy nanoparticles is 0.1-5% of the mass of the UiO-67; further preferably, the loading of the PdCo alloy nano-particles is 0.5% -3% of the mass of UiO-67.
Preferably, the molar ratio of Pd/Co in the PdCo alloy nano-particles is 9:1-1:9; further preferably, the molar ratio of Pd/Co in the PdCo alloy nanoparticles is from 2:1 to 1:2.
The invention also provides a preparation method of the UiO-67 encapsulated metal nanoparticle catalyst.
The preparation method of the UiO-67 encapsulated metal nanoparticle catalyst comprises the following steps:
1) Preparing a metal organic framework material UIO-67: dissolving zirconium salt and a polydentate carboxylic acid ligand in a solvent, and performing solvothermal reaction to obtain a metal-organic framework material UIO-67; the multidentate carboxylic acid ligand comprises bipyridine units;
2) Preparing a UiO-67 immobilized PdCO salt material: dissolving palladium salt and cobalt salt in a solvent, then adding the UiO-67, heating for reaction, carrying out solvent exchange on the obtained solid product, and drying to obtain a UiO-67 immobilized PdCO salt material;
3) Preparation of UiO-67 encapsulated metal nanoparticle catalyst: and heating the UiO-67 immobilized PdCO salt material under reducing gas to obtain the UiO-67 encapsulated metal nanoparticle catalyst.
Preferably, in step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the molar ratio of the zirconium salt, the polydentate carboxylic acid ligand, and the solvent is 1: (1-1.2): (400-1800); further preferably, the molar ratio of the zirconium salt, the polydentate carboxylic acid ligand, and the solvent is 1:1: (500-1700).
Preferably, in step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the zirconium salt comprises at least one of zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium oxychloride and zirconium acetate; further preferably, the zirconium salt is selected from at least one of zirconium chloride, zirconium nitrate, zirconium oxychloride.
Preferably, in step 1) of this UiO-67 encapsulated metal nanoparticle catalyst preparation method, the multidentate carboxylic acid ligand is selected from 2,2' -bipyridine-5, 5' -dicarboxylic acid, or the multidentate carboxylic acid ligand is a combination of 2,2' -bipyridine-5, 5' -dicarboxylic acid and 4,4' -biphthalic acid. When the multidentate carboxylic acid ligand is selected from the group consisting of 2,2 '-bipyridine-5, 5' -dicarboxylic acid and 4,4 '-biphthalic acid, the molar ratio of 2,2' -bipyridine-5, 5 '-dicarboxylic acid to 4,4' -biphthalic acid is preferably 1: (1-1.5).
Preferably, in step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the solvent comprises at least one of N, N-dimethylformamide, methanol, ethanol, isopropanol, tetrahydrofuran, dimethyl sulfoxide, acetone, diethyl ether and water; further preferably, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, ethanol, and water.
Preferably, in the step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the temperature of the solvothermal reaction is 60-150 ℃ and the time of the solvothermal reaction is 24-48 hours; further preferably, the solvothermal reaction is carried out at 100℃to 120℃for 24 hours to 48 hours.
Preferably, in step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the solvent thermal reaction further comprises the steps of filtering, washing and drying the obtained solid product. The drying is vacuum drying for 12-48 h at 100-200 ℃; further preferably, the drying is vacuum drying at 100℃to 150℃for 12 hours.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the palladium salt comprises at least one of palladium chloride, palladium nitrate, diacetonitrile palladium chloride and palladium acetylacetonate; the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the solvent used for dissolving the metal salt comprises at least one of acetonitrile, N-dimethylformamide and acetone; most preferably, in step 2), the solvent used to dissolve the metal salt is acetonitrile.
Preferably, in the step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the temperature of the heating reaction is 50-80 ℃, and the heating reaction time is 12-36 h; further preferably, the temperature of the heating reaction is 60-70 ℃, and the time of the heating reaction is 22-26 hours; most preferably, the heating reaction is a reaction at 65℃for 24h.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the step of filtering and washing the obtained solid product is further included before the solvent exchange.
Preferably, in step 2) of this preparation method of UiO-67 encapsulated metal nanoparticle catalyst, the solvent exchange is specifically carried out by immersing the washed solid product in an exchange solvent. The time for solvent exchange is preferably 3 days, with exchange solvent being exchanged every 24 hours. The exchange solvent is preferably at least one of ethyl acetate, acetone and chloroform.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the step of filtering and washing the product obtained by solvent exchange is further included before drying.
Preferably, in the step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the drying is carried out for 12-48 hours under vacuum at 100-200 ℃; most preferably, the drying is vacuum drying at 150 ℃ for 12 hours.
Preferably, in step 3) of the UiO-67 encapsulated metal nanoparticle catalyst preparation method, the reducing gas comprises at least one of hydrogen and carbon monoxide; further preferably, the reducing gas is selected from at least one of hydrogen and carbon monoxide; or a mixed gas of at least one of hydrogen and carbon monoxide and at least one of nitrogen, helium, neon and argon. The volume percentage of hydrogen and/or carbon monoxide in the mixed gas is preferably 5-10%.
Preferably, in step 3) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the heating reaction is specifically carried out at 300-400 ℃ for 0.5-2 h.
The invention also provides application of the UiO-67 encapsulated metal nanoparticle catalyst in an acetaldehyde catalytic oxidation reaction.
The reaction temperature of the acetaldehyde catalytic oxidation reaction is 20-250 ℃, preferably 80-220 ℃.
The beneficial effects of the invention are as follows:
in the UiO-67 encapsulated metal nanoparticle catalyst, the PdCo alloy nanoparticles are confined in the pore canal inner cavity of the UiO-67, and the particle size of the PdCo alloy nanoparticles is uniform and highly dispersed. The catalyst has very high activity and stability, and can be applied to the catalytic oxidation reaction of acetaldehyde to show excellent catalytic performance.
Compared with the prior art, the invention has the following advantages:
1) The invention takes the metal organic framework material UiO-67 as a carrier, utilizes the bipyridine units in the ligand to coordinate with metal ions, and the N atoms exposed in the bipyridine units are coupled and coordinated with the active component PdCo, so that the interaction force is strong. The method can lead the precursors of different metals to be uniformly distributed in the UiO-67 framework, so alloy particles are easier to form, and the interaction force of the different metals in the alloy particles is stronger. The chelation point and geometry on the UiO-67 ligand can synergistically limit the growth of alloy nanoparticles during the reduction process and confine them in the pore channels.
2) The high-dispersion limited domain PdCo@UiO-67 catalyst provided by the invention has excellent catalytic performance in an acetaldehyde catalytic oxidation reaction, and can be used for completely catalyzing and converting acetaldehyde at a low temperature, and compared with single metal or PdCo alloy particles deposited on the outer surface of the UiO-67, the catalyst has better synergistic effect and higher catalytic activity.
Drawings
FIG. 1 is Pd prepared in example 1 2 Co 1 TEM image of the @ UiO-67 catalyst;
FIG. 2 is a graph showing the results of performance tests of the catalysts prepared in examples and comparative examples.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The raw materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources unless otherwise specified. Unless otherwise indicated, assays or testing methods are routine in the art.
Example 1
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium chloride and 1mmol of 2,2 '-bipyridine-5, 5' -dicarboxylic acid are dissolved in 60mL of N, N-dimethylformamide, the mixture is reacted for 24 hours at 120 ℃, and the obtained solid product is filtered and washed and is dried in vacuum for 12 hours at 150 ℃ to obtain the metal-organic framework carrier material UIO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
A certain amount of diacetonitrile palladium chloride and cobalt nitrate are fully dissolved in 30mL of acetonitrile, then a metal organic framework carrier material UiO-67 is added, pd is controlled 2+ /Co 2+ Is 2:1, while the total metal content (Pd 2+ +Co 2+ ) The mass ratio to the carrier material UiO-67 was controlled at 2wt%. Reacting for 24 hours at the constant temperature of 65 ℃, cooling to room temperature, filtering and washing, immersing the solid in 30mL of ethyl acetate, replacing the ethyl acetate every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying for 12 hours at 150 ℃ to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo@UiO-67 catalyst
The UiO-67 immobilized PdCO salt material is placed in hydrogen atmosphere and heated for 2 hours at 300 ℃ to prepare Pd 2 Co 1 @UiO-67(2％)。
FIG. 1 is a Pd prepared in example 1 2 Co 1 TEM image of the @ UiO-67 catalyst.FIG. 1It is shown that the nano particles with the particle size of 2-6 nm are uniformly dispersed in the catalyst.
Example 2
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium chloride and 1mmol of 2,2 '-bipyridine-5, 5' -dicarboxylic acid are dissolved in 60mL of N, N-dimethylformamide, the mixture is reacted for 24 hours at 120 ℃, and the obtained solid product is filtered and washed and is dried in vacuum for 12 hours at 150 ℃ to obtain the metal-organic framework carrier material UIO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
A certain amount of diacetonitrile palladium chloride and cobalt acetate are fully dissolved in 30mL of acetonitrile, then a metal organic framework carrier material UiO-67 is added, pd is controlled 2+ /Co 2+ Is 2:1, while the total metal content (Pd 2+ +Co 2+ ) The mass ratio to the carrier material UiO-67 was controlled at 0.5wt%. Reacting for 24 hours at the constant temperature of 65 ℃, cooling to room temperature, filtering and washing, immersing the solid in 30mL of ethyl acetate, replacing the ethyl acetate every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying for 12 hours at 150 ℃ to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo@UiO-67 catalyst
The UiO-67 immobilized PdCO salt material is placed in carbon monoxide atmosphere and heated for 0.5h at 350 ℃ to prepare Pd 2 Co 1 @UiO-67(0.5％)。
Example 3
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium chloride and 1mmol of 2,2 '-bipyridine-5, 5' -dicarboxylic acid are dissolved in 60mL of N, N-dimethylformamide, the mixture is reacted for 24 hours at 120 ℃, and the obtained solid product is filtered and washed and is dried in vacuum for 12 hours at 150 ℃ to obtain the metal-organic framework carrier material UIO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
A certain amount of palladium nitrate and cobalt chloride are fully dissolved in 30mL of acetonitrile, then a metal organic framework carrier material UiO-67 is added, pd is controlled 2+ /Co 2+ Is 2:1, while the total metal content (Pd 2+ +Co 2+ ) The mass ratio to the carrier material UiO-67 was controlled at 5wt%. Reacting for 24 hours at the constant temperature of 65 ℃, cooling to room temperature, filtering and washing, immersing the solid in 30mL of ethyl acetate, replacing the ethyl acetate every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying for 12 hours at 150 ℃ to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo@UiO-67 catalyst
The UiO-67 immobilized PdCO salt material is placed in a mixed atmosphere of 5 percent hydrogen and 95 percent nitrogen by volume percent and heated for 2 hours at 400 ℃ to prepare Pd 2 Co 1 @UiO-67(5％)。
Example 4
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium oxychloride, 0.5mmol of 2,2' -bipyridine-5, 5' -dicarboxylic acid and 0.5mmol of 4,4' -biphenyl dicarboxylic acid are dissolved in 30mL of water, reacted at 100 ℃ for 36h, and the obtained solid product is filtered and washed and dried at 100 ℃ for 12h in vacuum to obtain the metal-organic framework carrier material UIO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
Palladium acetylacetonate and cobalt sulfate in certain amount are dissolved in 30mL acetonitrile, and then metal organic skeleton carrier material UiO-67 is added to control Pd 2+ /Co 2+ Is 1:1, while the total metal content (Pd 2+ +Co 2+ ) The mass ratio to the carrier material UiO-67 was controlled at 2wt%. Reacting for 24 hours at the constant temperature of 65 ℃, cooling to room temperature, filtering and washing, immersing the solid in 30mL of acetone, replacing the acetone every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying for 12 hours at 150 ℃ to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo@UiO-67 catalyst
The UiO-67 immobilized PdCO salt material is placed in a mixed atmosphere of 10 percent of carbon monoxide and 90 percent of helium by volume percent and heated for 1h at 400 ℃ to prepare Pd 1 Co 1 @UiO-67(2％)。
Example 5
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium nitrate, 0.4mmol of 2,2' -bipyridine-5, 5' -dicarboxylic acid and 0.6mmol of 4,4' -biphthalic acid are dissolved in 30mL of ethanol to react for 48h at 100 ℃, and the obtained solid product is filtered, washed and dried in vacuum for 12h at 100 ℃ to obtain the metal-organic framework carrier material UIO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
A certain amount of palladium chloride and cobalt chloride are fully dissolved in 30mL of acetonitrile, then a metal organic framework carrier material UiO-67 is added, pd is controlled 2+ /Co 2+ Is 1:2, while the total metal content (Pd 2+ +Co 2+ ) The mass ratio to the carrier material UiO-67 was controlled at 2wt%. Reacting for 24 hours at the constant temperature of 65 ℃, cooling to room temperature, filtering and washing, immersing the solid in 30mL of chloroform, replacing the chloroform every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying for 12 hours at 150 ℃ to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo@UiO-67 catalyst
The UiO-67 immobilized PdCO salt material is placed in a mixed atmosphere of 5 percent hydrogen and 95 percent argon by volume percent and heated for 2 hours at 400 ℃ to prepare Pd 1 Co 2 @UiO-67(2％)。
Comparative example 1
The preparation method of the UiO-67 encapsulated Pd nanoparticle catalyst Pd@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium nitrate, 0.45mmol of 2,2' -bipyridine-5, 5' -dicarboxylic acid and 0.55mmol of 4,4' -biphthalic acid are dissolved in 30mL of ethanol, the mixture is reacted for 48h at 100 ℃, and the obtained solid product is filtered and washed and dried in vacuum for 12h at 100 ℃ to obtain the metal-organic framework carrier material UIO-67.
2) Preparation of UiO-67 immobilized Pd salt material
A certain amount of diacetonitrile palladium chloride is fully dissolved in 30mL of acetonitrile, and then a metal organic framework carrier material UiO-67 and metal content Pd are added 2+ The mass ratio to the carrier material UiO-67 was controlled at 2wt%. Reacting for 24h at constant temperature of 65 ℃, cooling to room temperature, filtering and washing, putting the solid into 30mL of chloroformSoaking, replacing chloroform every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12 hours to obtain the metal organic framework material immobilized Pd salt material.
3) Preparation of Pd@UiO-67 catalyst
The UiO-67 immobilized Pd salt material is placed in a mixed atmosphere of 5% hydrogen and 95% argon by volume percent and heated at 400 ℃ for 2 hours to prepare Pd@UiO-67 (2%).
Comparative example 2
The preparation method of the UiO-67 encapsulated Co nanoparticle catalyst Co@UiO-67 comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
Dissolving 1mmol of zirconium nitrate, 0.6mmol of 2,2' -bipyridine-5, 5' -dicarboxylic acid and 0.4mmol of 4,4' -biphthalic acid in 30mL of ethanol, reacting at 100 ℃ for 48h, filtering and washing the obtained solid product, and vacuum drying at 100 ℃ for 12h to obtain a metal-organic framework carrier material UIO-67;
2) Preparation of UiO-67 immobilized Co salt material
A certain amount of cobalt nitrate is fully dissolved in 30mL of acetonitrile, and then a metal organic framework carrier material UiO-67 and metal content Co are added 2+ The mass ratio to the carrier material UiO-67 was controlled at 2wt%. Reacting for 24 hours at the constant temperature of 65 ℃, cooling to room temperature, filtering and washing, immersing the solid in 30mL of chloroform, replacing the chloroform every 24 hours, continuously exchanging for 3 days, filtering and washing, and vacuum drying for 12 hours at 150 ℃ to obtain the metal organic framework material immobilized Co salt material.
3) Preparation of Co@UiO-67 catalyst
The UiO-67 immobilized Co salt material is placed in a mixed atmosphere of 5% hydrogen and 95% argon by volume percent and heated for 2 hours at 400 ℃ to prepare Co@UiO-67 (2%).
Comparative example 3
A method for preparing a catalyst PdCo/UiO-67 by depositing PdCo alloy nano particles on the outer surface of the UiO-67, which comprises the following steps:
1) Preparation of a Metal organic framework Carrier Material UiO-67
1mmol of zirconium chloride and 1mmol of 4,4' -biphenyl dicarboxylic acid are dissolved in 60mL of N, N-dimethylformamide and reacted for 24 hours at 120 ℃, and the obtained solid product is filtered and washed and dried in vacuum for 12 hours at 150 ℃ to obtain a metal-organic framework carrier material UIO-67.
2) Preparation of metal organic framework material UiO-67 loaded PdCo salt material
A certain amount of diacetonitrile palladium chloride and cobalt nitrate are fully dissolved in 30mL of acetonitrile, then a metal organic framework carrier material UiO-67 is added, pd is controlled 2+ /Co 2+ Is 2:1, while the total metal content (Pd 2+ +Co 2+ ) The mass ratio to the carrier material UiO-67 was controlled at 2wt%. And (3) immersing for 24 hours at room temperature, evaporating to remove acetonitrile, and vacuum drying at 150 ℃ for 12 hours to obtain the UiO-67 loaded PdCO salt material.
3) Preparation of PdCo/UIO-67
And (3) placing the UiO-67 loaded PdCO salt material in a mixed atmosphere of 5% hydrogen and 95% argon in volume percentage, and heating at 400 ℃ for 2 hours to obtain the PdCO/UiO-67.
Application testing
1. The catalysts prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to an acetaldehyde catalytic oxidation performance test.
The test conditions were as follows: the concentration of the reaction raw material gas is 10mg/m 3 The total flow rate of the acetaldehyde simulation gas is 25mL/min, the catalyst size is 40-60 meshes, the filling amount is 100mg, and the space velocity is 15000mL/g/h.
The test method is as follows: the reaction raw material gas passes through a quartz tube reactor filled with a catalyst, the quartz tube reactor is placed in a temperature control furnace to control the reaction temperature, and after the reaction gas reacts for 20min at a certain temperature, the gas detects the concentration of the outlet acetaldehyde on line through a gas chromatograph. The catalyst was tested three times at each temperature and averaged to calculate the conversion of acetaldehyde at each temperature to represent the catalytic activity of the catalyst on acetaldehyde.
The results of the catalyst performance test are shown in figure 2.
As can be seen from fig. 2: under the test conditions, the UiO-67 encapsulated PdCO alloy nanoparticle catalyst prepared by the method has better reaction activity than the single metal catalyst in comparative examples 1-2. The catalyst prepared in example 1 achieves complete conversion of acetaldehyde at 100 ℃, whereas the catalyst prepared in comparative example 1 achieves complete conversion of acetaldehyde only at 150 ℃, and the catalyst prepared in comparative example 2 achieves complete conversion of acetaldehyde at temperatures even higher than 200 ℃. This is mainly due to the lack of intermetallic synergism in the single metal catalysts.
As can also be seen from fig. 2: under the test conditions, the UiO-67 encapsulated PdCO alloy nanoparticle catalyst prepared by the method has better reaction activity than the supported PdCO/UiO-67 catalyst in comparative example 3. The catalyst prepared in comparative example 3 was required to convert acetaldehyde completely at 180 ℃. This is mainly because the preparation method in comparative example 3 is an impregnation method, and the supported PdCo alloy nanoparticles are mainly deposited on the surface of the UiO-67 carrier, and are easily migrated during the preparation and reaction processes to undergo agglomeration and sintering, thereby greatly reducing the activity.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. Use of a UiO-67 encapsulated metal nanoparticle catalyst in an acetaldehyde catalytic oxidation reaction, the catalyst comprising a support and an active component, characterized in that: the carrier is a metal organic framework material UiO-67, and the active component is PdCo alloy nano particles; the PdCo alloy nanoparticles are confined in the inner cavity of the UiO-67 framework; the loading amount of the PdCo alloy nano particles is 2% -3% of the mass of UiO-67; the molar ratio of Pd/Co in the PdCo alloy nano-particles is 2:1-1:2;
the UiO-67 encapsulated metal nanoparticle catalyst is prepared by a preparation method comprising the following steps:
1) Preparing a metal organic framework material UIO-67: dissolving zirconium salt and a polydentate carboxylic acid ligand in a solvent, and performing solvothermal reaction to obtain a metal-organic framework material UIO-67; the multidentate carboxylic acid ligand comprises bipyridine units; the multidentate carboxylic acid ligand is selected from 2,2' -bipyridine-5, 5' -dicarboxylic acid, or the multidentate carboxylic acid ligand is a combination of 2,2' -bipyridine-5, 5' -dicarboxylic acid and 4,4' -biphthalic acid;
2) Preparing a UiO-67 immobilized PdCO salt material: dissolving palladium salt and cobalt salt in a solvent, then adding the UiO-67, heating for reaction, carrying out solvent exchange on the obtained solid product, and drying to obtain a UiO-67 immobilized PdCO salt material; the solvent used for dissolving the metal salt comprises at least one of acetonitrile, N-dimethylformamide and acetone; the temperature of the heating reaction is 50-80 ℃; the heating reaction time is 12-36 h;
3) Preparation of UiO-67 encapsulated metal nanoparticle catalyst: and heating the UiO-67 immobilized PdCO salt material under reducing gas to obtain the UiO-67 encapsulated metal nanoparticle catalyst.
2. The use according to claim 1, characterized in that: in the step 1), the molar ratio of the zirconium salt, the polydentate carboxylic acid ligand and the solvent is 1: (1-1.2): (400-1800).
3. Use according to claim 1 or 2, characterized in that: in the step 1), the zirconium salt comprises at least one of zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium oxychloride and zirconium acetate.
4. Use according to claim 1 or 2, characterized in that: in the step 1), the solvent comprisesN,N-at least one of dimethylformamide, methanol, ethanol, isopropanol, tetrahydrofuran, dimethyl sulfoxide, acetone, diethyl ether, water.
5. The use according to claim 1, characterized in that: in the step 1), the temperature of the solvothermal reaction is 60-150 ℃.
6. The use according to claim 1, characterized in that: in the step 1), the solvothermal reaction time is 24-48 h.
7. The use according to claim 1, characterized in that: in the step 2), the palladium salt comprises at least one of palladium chloride, palladium nitrate, diacetonitrile palladium chloride and palladium acetylacetonate.
8. The use according to claim 1, characterized in that: in the step 2), the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
9. The use according to claim 1, characterized in that: in the step 3), the reducing gas contains at least one of hydrogen and carbon monoxide.
10. The use according to claim 1, characterized in that: in the step 3), the heating reaction is specifically carried out at 300-400 ℃ for 0.5-2 h.
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| Bimetallic synergy in cobalt–palladium nanocatalysts for CO oxidation;Cheng Hao Wu等;《NATURE CATALYSIS》;20190131;第2卷;第78-85页 * |
| On thermal stability and catalytic reactivity of Zr-based metal–organic framework (UiO-67) encapsulated Pt catalysts;Peter Hester等;《Journal of Catalysis》;20161231;第340卷;第85-94页 * |
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