CN113769783B - Preparation method of bamboo-shaped core-shell photo-thermal catalyst - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011258 core-shell material Substances 0.000 title claims abstract description 18
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 239000002071 nanotube Substances 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- -1 1-propylsulfo-3-vinylimidazolium bisulfate Chemical group 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 241000080590 Niso Species 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- KXYSPMWKPGPHTD-UHFFFAOYSA-M [Br-].C(C)[P+](C1=CC=C(C=C1)C=C)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Br-].C(C)[P+](C1=CC=C(C=C1)C=C)(C1=CC=CC=C1)C1=CC=CC=C1 KXYSPMWKPGPHTD-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 2
- PREZSYXZLYLHNH-UHFFFAOYSA-M 1-ethenyl-3-ethylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C=C)=C1 PREZSYXZLYLHNH-UHFFFAOYSA-M 0.000 claims description 2
- YSOJAHDVFUYJHT-UHFFFAOYSA-M 1-ethenyl-3-ethylimidazol-3-ium;chloride Chemical compound [Cl-].CCN1C=C[N+](C=C)=C1 YSOJAHDVFUYJHT-UHFFFAOYSA-M 0.000 claims description 2
- UOARFFHPYSKBNB-UHFFFAOYSA-M 1-ethenyl-3-ethylimidazol-3-ium;iodide Chemical compound [I-].CCN1C=C[N+](C=C)=C1 UOARFFHPYSKBNB-UHFFFAOYSA-M 0.000 claims description 2
- MDGYSMXXCXVZSY-UHFFFAOYSA-M 2-(3-ethenylimidazol-1-ium-1-yl)ethanamine bromide Chemical compound [Br-].NCC[n+]1ccn(C=C)c1 MDGYSMXXCXVZSY-UHFFFAOYSA-M 0.000 claims description 2
- IWIVGKAKBWXINR-UHFFFAOYSA-M 2-(3-ethenylimidazol-1-ium-1-yl)ethanol;bromide Chemical compound [Br-].OCC[N+]=1C=CN(C=C)C=1 IWIVGKAKBWXINR-UHFFFAOYSA-M 0.000 claims description 2
- HLTAVCXCPIJAPU-UHFFFAOYSA-M 2-(3-ethenylimidazol-1-ium-1-yl)ethanol;chloride Chemical compound [Cl-].OCCN1C=C[N+](C=C)=C1 HLTAVCXCPIJAPU-UHFFFAOYSA-M 0.000 claims description 2
- IAHAKYOZOQLXPG-UHFFFAOYSA-N 4-(3-ethenylimidazol-1-ium-1-yl)butanoic acid bromide Chemical compound [Br-].C(=O)(O)CCC[N+]1=CN(C=C1)C=C IAHAKYOZOQLXPG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- LCFKXCNZLIBDOX-UHFFFAOYSA-L dihydrogen phosphate;nickel(2+) Chemical compound [Ni+2].OP(O)([O-])=O.OP(O)([O-])=O LCFKXCNZLIBDOX-UHFFFAOYSA-L 0.000 claims description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims 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 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 230000002195 synergetic effect Effects 0.000 abstract description 9
- 238000000197 pyrolysis Methods 0.000 abstract description 6
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 6
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000006352 cycloaddition reaction Methods 0.000 description 4
- 239000002079 double walled nanotube Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000006053 organic reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- JVRWQHCUISDRGA-UHFFFAOYSA-N 1-ethenyl-3-ethyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCN1C[NH+](C=C)C=C1 JVRWQHCUISDRGA-UHFFFAOYSA-N 0.000 description 2
- SLDMVNLFJWRODV-UHFFFAOYSA-N 1-ethenyl-3-ethyl-1,2-dihydroimidazol-1-ium;iodide Chemical compound [I-].CCN1C[NH+](C=C)C=C1 SLDMVNLFJWRODV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 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 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
-
- B01J35/39—
Abstract
The invention relates to a preparation method of a bamboo-shaped core-shell photo-thermal catalyst. The method comprises the steps of derivatizing dodecahedral monocrystal ZIF-ZnNi into bamboo-like hollow Ni-N-C nanotubes by a ZIF plus metal nickel salt pyrolysis method; then coating the functionalized ionic liquid on the surface of the Ni-N-C nanotube by using a dip-coating-in-situ polymerization method to form a bamboo-like Ni-N-C@ polyionic liquid compound; finally, the polyion liquid is super-crosslinked to form mesopores through Friedel-Crafts alkylation reaction, so that the bamboo-like core-shell photo-thermal catalyst is obtained. The invention has great potential application value in the fields of photo-thermal catalysis, synergetic catalysis and the like, and widens the application of the invention in the catalysis field.
Description
Technical Field
The technical scheme of the invention relates to the fields of polyionic liquids, metal organic framework compounds (MOFs) and single-atom materials derived from the MOFs, in particular to a preparation method of a bamboo-shaped core-shell photo-thermal catalyst.
Background
In recent years, monoatomic catalysts have attracted considerable attention in the catalytic field due to their high atom utilization, excellent selectivity and catalytic activity (Chem 2019,5 (4), 786-804). CO with monoatomic catalyst 2 Photocatalytic conversion into value-added chemicals and fuels has shown great potential for application in addressing energy crisis and alleviating greenhouse effects and has been of great interest (Nat. Energy 2021,6,807-814). The zeolite imidazole ester skeleton (ZIF) is used as a subclass of MOFs materials, and is an ideal precursor for preparing a single-atom catalyst (Nano Energy 2020,71,104547) due to higher nitrogen content, ordered pore structure and flexible and changeable metal sites. Various metal monoatomic catalysts (Ni, fe, co, zn, etc.) can be prepared by the strategy of pyrolysis of ZIFs (adv. Energy mater.2020, 10 (38), 2001561). However, most of the ZIF derived monoatomic catalysts reported at present have a structure of micron-sized rhombic dodecahedron and are microporous<2 nm) structure is mainly used, so that the catalyst can only use single atomic sites on the surface when participating in catalysis, the active sites embedded in the catalyst cannot be effectively utilized, and the atomic utilization rate (Chem 2020,6 (1), 19-40) is reduced. Constructing ZIF-derived monoatomic catalysts into nanoscale monodisperse nanotube structures is considered an effective method of improving atom utilization (adv.funct.mater.2021, 31,2010472). The nano tubular structure not only can expose the internal active site and improve the mass transfer efficiency, but also expands the application of the material in catalysis involving large-size compoundsImportant pathways (adv. Mate. 2019, 31 (49), 1906051). Although a few ZIF-derived bamboo-like nanotubes have been reported, dicyandiamide, melamine, etc. are required to be added in the preparation process, and these reagents are easy to form highly toxic cyanide (Small 2020,16 (41), 2002124) during pyrolysis at high temperature. Therefore, the development of a new method for preparing the ZIF-derived bamboo-like nano tube, which is convenient and environment-friendly, has important research significance.
Because of the unique electronic structure, coordination environment, size effect, metal-carrier interaction and other advantages of the metal monoatomic catalyst, most of researches are focused on the fields of electrocatalysis and the like, but the application of the metal monoatomic catalyst in organic reactions with complex reaction mechanisms is rarely reported (Small 2021,17,2004809). In order for a single-atom catalyst to complete a complex organic reaction, it is often necessary to add a homogeneous promoter for the synergistic catalysis, which however complicates the separation of the catalyst and the purification of the product (angel. Chem. Int. Ed.2019,58 (11), 3511-3515). Therefore, the single-atom catalyst and the functional site (chemical group) with the auxiliary catalytic performance are integrated, so that the bionic catalyst with the synergistic effect of the double-functional site can be constructed, and the application of the single-atom catalyst in complex organic reactions can be possibly expanded.
The patent designs and prepares dodecahedral monocrystal ZIF-ZnNi, prepares a bamboo-shaped hollow Ni-N-C nano tube by adopting high-temperature pyrolysis, and prepares a bamboo-shaped core-shell photo-thermal catalyst by utilizing dip-coating-in-situ polymerization and super-crosslinking strategies. The catalyst combines the core-shell structure, the bamboo-like hollow nano-tube structure and the Lewis acidity/nucleophile characteristic together, so that the material can catalyze and convert CO 2 Has excellent development prospect for value-added products.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a preparation method of a bamboo-shaped core-shell photo-thermal catalyst. The method comprises the steps of derivatizing dodecahedral monocrystal ZIF-ZnNi into bamboo-shaped hollow Ni-N-C nanotubes (simultaneously generating Ni nano particles and Ni single atoms) by a ZIF plus metal nickel salt pyrolysis method; then coating the functionalized ionic liquid on the surface of the Ni-N-C nanotube by using a dip-coating-in-situ polymerization method to form a bamboo-like Ni-N-C@ polyionic liquid compound; finally, the polyionic liquid is super-crosslinked to form mesopores through Friedel-Crafts alkylation reaction, so that the bamboo-shaped core-shell photo-thermal catalyst (bamboo-shaped Ni-N-C@ mesoporous polyionic liquid) is obtained. The invention has great potential application value in the fields of photo-thermal catalysis, synergetic catalysis and the like, and widens the application of the invention in the catalysis field.
The technical scheme of the invention is as follows:
the preparation method of the bamboo-shaped core-shell photo-thermal catalyst comprises the following steps:
1) Preparation of dodecahedral single crystals ZIF-ZnNi having an average particle diameter in the range of 100nm to 3 mu m
Dissolving 2-methylimidazole in absolute methanol to obtain a first solution; zn (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is dissolved in absolute methanol to obtain a second solution; then pouring the first solution into the second solution, magnetically stirring for 10-60 min at 25 ℃, standing for 6-24 h to complete crystallization, centrifugally settling the material after the reaction is finished, washing with methanol, and drying in vacuum to obtain dodecahedral monocrystal ZIF-ZnNi;
wherein, every 120mL of absolute methanol in the first solution is added with 0.05-3.0 mol of 2-methylimidazole; adding 0.001-0.4 mol Zn (NO) into every 120mL absolute methanol in the second solution 3 ) 2 ·6H 2 O and 0.001 to 0.4mol of Ni (NO) 3 ) 2 ·6H 2 O; the molar ratio is that 2-methylimidazole: (Zn (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 Sum of O) =1: 0.05 to 1; molar ratio of Zn (NO) 3 ) 2 ·6H 2 O：Ni(NO 3 ) 2 ·6H 2 O＝1：0.05～1；
2) Preparation of bamboo-like Ni-N-C nano tube
Grinding the dodecahedron monocrystal ZIF-ZnNi obtained in the last step and metallic nickel salt for 10-60 min, then placing the ground dodecahedron monocrystal ZIF-ZnNi and metallic nickel salt into a quartz boat, and placing the quartz boat into a tube furnace at 2-5 ℃ for min -1 Raising the temperature from room temperature to 800-1100 ℃, keeping for 1-3 h, and naturally cooling to room temperature;
wherein, the amount of the metal nickel salt corresponding to each 1g of single crystal ZIF-ZnNi is 0.2-4 g;
the metal nickel salt is Ni (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 、NiSO 4 、NiCl 2 ·6H 2 O、NiCl 2 Nickel acetate tetrahydrate (C) 4 H 14 NiO 8 )、Ni(CH 3 COO) 2 Nickel phosphate, nickel dihydrogen phosphate, basic nickel carbonate, nickel sulfamate or nickel bromide.
3) Bamboo-like Ni-N-C nanotube surface coated polyion liquid
Dropwise adding an ethanol mixed solution containing a functionalized ionic liquid monomer, a cross-linking agent and azodiisobutyronitrile into the prepared bamboo-like Ni-N-C, then reacting at 70-80 ℃ for 12-24 h, and then reacting at 90-100 ℃ for 10-24 h; the bamboo-like Ni-N-C@ mesoporous polyion liquid can be obtained;
wherein, each 1g of the bamboo-like Ni-N-C corresponding mixed solution is 0.1 to 15g; the mass ratio of the mixed solution is that the functionalized ionic liquid monomer: crosslinking agent: azobisisobutyronitrile: ethanol=0.1 to 2:0.1: 0.005-0.05: 0.5 to 3;
the cross-linking agent is divinylbenzene or 4-chloromethyl styrene;
the functionalized ionic liquid-containing monomer is 1-propylsulfo-3-vinylimidazolium bisulfate, 1- (3 ' -carboxypropyl) -3-vinylimidazolium bromide, 1- (2 ' -aminoethyl) -3-vinylimidazolium bromide, 1-ethyl-3-vinylimidazolium bromide, 1- (2 ' -hydroxyethyl) -3-vinylimidazolium bromide, ethyldiphenyl (4-vinylphenyl) phosphonium bromide, 1- (3 ' -carboxypropyl) -3-vinylimidazolium iodide, 1- (2 ' -aminoethyl) -3-vinylimidazolium iodide, 1-ethyl-3-vinylimidazolium iodide, 1- (2 ' -hydroxyethyl) -3-vinylimidazolium iodide, 1- (3 ' -carboxypropyl) -3-vinylimidazolium chloride, 1- (2 ' -aminoethyl) -3-vinylimidazolium chloride, 1-ethyl-3-vinylimidazolium chloride or 1- (2 ' -hydroxyethyl) -3-vinylimidazolium chloride;
4) Super-crosslinking mesoporous preparation method of polyion liquid
Adding the prepared bamboo-like Ni-N-C@ polyion liquid into 1, 2-dichloroethane, soaking for 1-4 h at 40-60 ℃, then adding anhydrous ferric trichloride, heating to 80-100 ℃ for reacting for 10-24 h, washing with ethanol after the reaction is finished, centrifuging, separating and drying to obtain the bamboo-like Ni-N-C@ mesoporous polyion liquid.
Wherein, 5 to 20g of 1, 2-dichloroethane and 0.1 to 0.3g of anhydrous ferric trichloride are added into each 0.1g of bamboo-like Ni-N-C nanotube surface coated polyion liquid.
The invention has the substantial characteristics that:
when catalyzing complex organic reactions, the high-activity metal monoatoms often need to add homogeneous cocatalysts (functional groups), which complicates the separation of the catalyst and the purification of the product. The invention integrates the functional polyion liquid and the high-activity metal single atom into the double-wall nano tube, and simultaneously increases the photo-thermal conversion capability by utilizing the plasma/magnetic Ni nano particles to form a truly heterogeneous photo-thermal catalyst.
The beneficial effects of the invention are as follows:
(1) The invention provides a method for conveniently preparing ZIF-derived bamboo-like Ni-N-C nanotubes. It can be seen from FIGS. 5 and 6 that the prepared bamboo-like Ni-N-C nanotubes have both Ni nanoparticles and Ni monoatoms. Compared with the traditional micron-sized rhombic dodecahedron structure, the bamboo-shaped nano tube is easy to expose more internal active sites and improves mass transfer efficiency. The preparation method is novel, and the process is simple and easy to implement.
(2) The invention makes full use of the characteristic that the ionic liquid is easy to compound and structure and the porous characteristic of the bamboo-shaped Ni-N-C nano tube, so that the ionic liquid and the bamboo-shaped Ni-N-C nano tube are reasonably distributed in the nano space. The ionic liquid is polymerized on the surface of the bamboo-shaped Ni-N-C nano tube by utilizing a dip-coating-in-situ polymerization strategy, so that a nano shell layer is formed. Then, the polyionic liquid is super-crosslinked to form mesopores through Friedel-Crafts alkylation reaction. Compared with the traditional mesoporous polyionic liquid (micron-sized particles), the mesoporous polyionic liquid with the nanoscale thickness greatly reduces mass transfer resistance. In addition, different functional polyionic liquids can be obtained by changing the types of the ionic liquids containing double bonds. Therefore, the method can be expanded to prepare other functionalized mesoporous polyionic liquids, and the obtained material has great potential application value in the aspect of catalytic reaction. The performance, structure and preparation thought of the material are not reported in novel documents.
(3) The invention is inspired by acid-base synergistic catalysis, takes monoatomic Ni-N-C as an inner wall, takes mesoporous polyion liquid as a shell layer, realizes the rational design and controllable preparation of the double-functional double-wall nanotube, wherein the mesoporous polyion liquid provides halogen ions, and the monoatomic Ni-N-C provides Lewis acid centers. On one hand, the characteristics that the micropore@mesoporous double-wall nanotube is easy to expose more internal active sites and improves mass transfer efficiency are utilized; on the other hand, the Lewis acid@nucleophile which is spatially distributed is utilized to increase the synergistic catalytic capability, so that the acid-base synergistic catalytic capability is further improved. In addition, the plasma/magnetic Ni nano particles can not only increase the photo-thermal conversion capability, but also improve the photo-catalytic efficiency; and is favorable for the recovery and separation of the catalyst, thereby improving the circulating catalytic capability of the catalyst. The prepared bamboo-like core-shell photo-thermal catalyst photo-drives CO 2 The cycloaddition reaction with epoxybromopropane shows excellent catalytic performance, and the catalytic yield is 99% under mild conditions (no solvent, no cocatalyst, normal pressure and light irradiation) as measured by a nuclear magnetic resonance spectrometer. However, the catalysts reported in the literature must be completed under relatively severe conditions (at least one of the addition of organic solvents, the addition of homogeneous promoters, high temperature and pressure, etc.) in order to achieve the same catalytic yields. The invention is easy to realize large-scale and industrialized production when in use, and has better industrial development prospect.
Drawings
Fig. 1: a preparation flow chart of the bamboo-shaped core-shell photo-thermal catalyst;
fig. 2: SEM photograph of dodecahedral single crystal ZIF-ZnNi of example 1;
fig. 3: SEM photograph of bamboo-like Ni-N-C nanotubes of example 1;
fig. 4: HAADF-STEM photograph of bamboo-like Ni-N-C nanotubes in example 1;
fig. 5: SEM photograph of bamboo-like Ni-N-C@ mesoporous polyionic liquid in example 1;
fig. 6: TEM photograph of bamboo-like Ni-N-C@ mesoporous polyionic liquid in example 1;
fig. 7: CO catalysis by bamboo-like Ni-N-C@ mesoporous polyionic liquid in example 1 2 Nuclear magnetic spectrum after cycloaddition reaction with epoxybromopropane.
Detailed Description
The preparation flow of the invention is shown in figure 1, (1) Zn (NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 Preparing dodecahedron single crystal ZIF-ZnNi by coordination polymerization by taking a methanol solution of O and 2-methylimidazole as precursors, (2) grinding the dodecahedron single crystal ZIF-ZnNi and a metal nickel salt and then carrying out pyrolysis to obtain bamboo-shaped Ni-N-C nanotubes, (3) coating the surfaces of the bamboo-shaped Ni-N-C nanotubes with functionalized polyion liquid, and (4) carrying out Friedel-Crafts alkylation reaction to ensure that the polyion liquid is super-crosslinked to form mesopores to form the bamboo-shaped nuclear shell photo-thermal catalyst.
The preparation process is simple, the large-scale preparation is easy, the obtained product has excellent photo-thermal conversion performance and high-activity multifunctional sites, and the microporous@mesoporous double-wall nanotube is easy to expose more internal active sites and improves the mass transfer efficiency; the Lewis acid@organic group is favorable for increasing the synergistic catalytic capability, and the characteristics lead the micro-nano reactor, the synergistic catalysis and other fields to have great potential application value.
Wherein the metallic nickel salt Ni (NO 3 ) 2 、NiSO 4 And functionalized ionic liquid monomer 1-vinyl-3-ethylimidazole bromide, ethyldiphenyl (4-vinylphenyl) phosphonium bromide and 1-vinyl-3-ethylimidazole iodide, which are known materials.
Example 1:
(1) Preparation of dodecahedral single crystal ZIF-ZnNi with particle size of about 300nm
0.44mol of 2-methylimidazole was dissolved in 120mL of absolute methanol in a 250mL beaker A, and 0.04mol of Zn (NO) was dissolved in another 250mL beaker B 3 ) 2 ·6H 2 O and 0.003mol of Ni (NO 3 ) 2 ·6H 2 O was dissolved in 120mL of anhydrous methanol. The solution in beaker A was poured rapidly into beaker B and magnetically stirred at 25℃for 30And (3) min, standing for 10h to complete crystallization, centrifuging and settling the material after the reaction is finished, washing the material with methanol for 3 times, and vacuum drying at 80 ℃ to obtain dodecahedral monocrystal ZIF-ZnNi.
FIG. 2 is a SEM photograph of a dodecahedral single crystal ZIF-ZnNi scanned with a scanning electron microscope model FEI Nano SEM 450, from which it can be seen that the single crystal ZIF-ZnNi exhibits a rhombic dodecahedral structure and has a size of about 300nm.
(2) Preparation of bamboo-like Ni-N-C nano tube
1g of dodecahedral single crystal ZIF-ZnNi was mixed with 0.2g of Ni (NO 3 ) 2 Grinding for 10min, placing into quartz boat, and placing into tube furnace at 3deg.C for min -1 And (3) raising the temperature from room temperature to 1000 ℃ and keeping for 2 hours, and naturally cooling to room temperature to obtain the bamboo-like Ni-N-C nano tube.
FIG. 3 is an SEM photograph of a bamboo-like Ni-N-C nanotube scanned by a scanning electron microscope model FEI Nano SEM 450, and it can be seen that the material exhibits a bamboo-like hollow nanostructure. Furthermore, the formation of Ni nanoparticles (white particles) can also be seen from the figure.
FIG. 4 is a spherical aberration correcting HAADF-STEM photograph of a bamboo-like Ni-N-C nanotube characterized by a spherical aberration correcting transmission electron microscope model Titan Themis Cubed G, 2, 60-300, from which it can be seen that Ni atoms exist in a monoatomic dispersed form.
(3) Bamboo-like Ni-N-C nanotube surface coated polyion liquid
Dropwise adding a mixed solution containing 0.5g of 1-vinyl-3-ethylimidazole bromide, 0.1g of divinylbenzene, 0.005g of azobisisobutyronitrile and 1.0g of ethanol into 0.2g of bamboo-like Ni-N-C prepared in the step (2), and then reacting at 80 ℃ for 12 hours and at 90 ℃ for 24 hours; the bamboo-shaped Ni-N-C nanotube@polyionic liquid core-shell structure composite material can be obtained.
(4) Super-crosslinking mesoporous preparation method of polyion liquid
Adding 0.1g of bamboo-like Ni-N-C nanotube @ polyion liquid prepared in the step (3) into 10g of 1, 2-dichloroethane, soaking for 1h at 40 ℃, then adding 0.3g of anhydrous ferric trichloride, and heating to 90 ℃ for reaction for 12h. Washing 3 times with ethanol after the reaction is finished, and drying for 12 hours at 80 ℃ after centrifugal separation to obtain the bamboo-like Ni-N-C@ mesoporous polyion liquid.
Fig. 5 is an SEM photograph obtained by scanning the bamboo-like Ni-N-C@ mesoporous polyionic liquid with a scanning electron microscope of the model FEI Nano SEM 450, and it can be seen from the figure that the surface of the material shows a rough structure after coating the polyionic liquid.
Fig. 6 is a TEM photograph obtained by characterizing a bamboo-like Ni-N-C nanotube with a FEI Talos F200S transmission electron microscope model, and it can be seen from the figure that the material exhibits a core-shell tubular structure, and Ni nanoparticles remain inside the bamboo-like structure.
FIG. 7 is a schematic illustration of a bamboo-like Ni-N-C@ mesoporous polyionic liquid catalyzed CO 2 Nuclear magnetic spectrum after cycloaddition reaction with epoxybromopropane. The cycloaddition reaction conditions are as follows: catalyst (20 mg), epibromohydrin (10 mmol), CO 2 (1 atm), xenon lamp full spectrum irradiation (0.4W/cm 2 ) The reaction was magnetically stirred in a glass vial for 12h without solvent and without cocatalyst. FIG. 7 shows a nuclear magnetic resonance spectrum showing CO after the catalytic reaction is completed 2 And completely reacts with epoxybromopropane to generate corresponding cyclic carbonate.
Example 2:
(1) Preparation of dodecahedral single crystals ZIF-ZnNi having a particle size of about 2. Mu.m
0.15mol of 2-methylimidazole was dissolved in 120mL of absolute methanol in a 250mL beaker A, and 0.04mol of Zn (NO) was dissolved in another 250mL beaker B 3 ) 2 ·6H 2 O and 0.003mol of Ni (NO 3 ) 2 ·6H 2 O was dissolved in 120mL of anhydrous methanol. Pouring the solution in the beaker A into a beaker B quickly, magnetically stirring for 30min at 25 ℃, standing for 10h to complete crystallization, centrifugally settling the material after the reaction is finished, washing the material with methanol for 3 times, and drying in vacuum at 80 ℃ to obtain dodecahedral monocrystal ZIF-ZnNi.
(2) The preparation of the bamboo-like Ni-N-C nanotubes was the same as in the step (2) of example 1.
(3) The preparation of the polyion liquid coated on the surface of the bamboo-like Ni-N-C nano tube is the same as that in the step (3) of the embodiment 1.
(4) The preparation of the polyionic liquid super-crosslinked mesoporous is the same as the step (4) of the example 1.
Example 3:
(1) A dodecahedral single crystal ZIF-ZnNi having a particle diameter of about 300nm was prepared in the same manner as in step (1) of example 1.
(2) The preparation of the bamboo-like Ni-N-C nanotubes was the same as in the step (2) of example 1.
(3) Bamboo-like Ni-N-C nanotube surface coated polyion liquid
Dropwise adding a mixed solution containing 0.5g of ethyldiphenyl (4-vinylphenyl) phosphorus bromide, 0.1g of divinylbenzene, 0.005g of azobisisobutyronitrile and 1.0g of ethanol into 0.2g of bamboo-like Ni-N-C prepared in the step (2), and then reacting at 80 ℃ for 12 hours and at 90 ℃ for 24 hours; the polyion liquid coated on the surface of the bamboo-like Ni-N-C nano tube can be obtained.
(4) The preparation of the polyionic liquid super-crosslinked mesoporous is the same as the step (4) of the example 1.
Example 4:
(1) A dodecahedral single crystal ZIF-ZnNi having a particle diameter of about 300nm was prepared in the same manner as in step (1) of example 1.
(2) Preparation of bamboo-like Ni-N-C nano tube
1g of dodecahedral single crystal ZIF-ZnNi is mixed with 0.3g of NiSO 4 Grinding for 10min, placing into quartz boat, and placing into tube furnace at 3deg.C for min -1 And (3) raising the temperature from room temperature to 1000 ℃ and keeping for 2 hours, and naturally cooling to room temperature to obtain the bamboo-like Ni-N-C nano tube.
(3) The preparation of the polyion liquid coated on the surface of the bamboo-like Ni-N-C nano tube is the same as that in the step (3) of the embodiment 1.
(4) The preparation of the polyionic liquid super-crosslinked mesoporous is the same as the step (4) of the example 1.
Example 5:
(1) A dodecahedral single crystal ZIF-ZnNi having a particle diameter of about 300nm was prepared in the same manner as in step (1) of example 1.
(2) The preparation of the bamboo-like Ni-N-C nanotubes was the same as in the step (2) of example 1.
(3) Bamboo-like Ni-N-C nanotube surface coated polyion liquid
Dropwise adding a mixed solution containing 0.5g of 1-vinyl-3-ethylimidazole iodide, 0.1g of divinylbenzene, 0.005g of azobisisobutyronitrile and 1.0g of ethanol into 0.2g of bamboo-like Ni-N-C prepared in the step (2), then reacting at 80 ℃ for 12 hours, and reacting at 90 ℃ for 24 hours; the polyion liquid coated on the surface of the bamboo-like Ni-N-C nano tube can be obtained.
(4) The preparation of the polyionic liquid super-crosslinked mesoporous is the same as the step (4) of the example 1.
The invention is not a matter of the known technology.
Claims (4)
1. The preparation method of the bamboo-shaped core-shell photo-thermal catalyst is characterized by comprising the following steps of:
1) Preparation of dodecahedral single crystal ZIF-ZnNi with average particle diameter ranging from 100nm to 3 mu m
Dissolving 2-methylimidazole in absolute methanol to obtain a first solution; zn (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is dissolved in absolute methanol to obtain a second solution; the first solution is then poured into the second solution at 25 o Magnetically stirring for 10-60 min under the condition of C, standing for 6-24 h to finish crystallization, centrifugally settling the material after the reaction is finished, washing with methanol, and drying in vacuum to obtain dodecahedron monocrystal ZIF-ZnNi;
wherein 0.05-3.0 mol of 2-methylimidazole is added into every 120-mL absolute methanol in the first solution; adding 0.001-0.4 mol of Zn (NO) into every 120-mL absolute methanol in the second solution 3 ) 2 ·6H 2 O and 0.001 to 0.4mol of Ni (NO) 3 ) 2 ·6H 2 O; the molar ratio is that 2-methylimidazole: (Zn (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 Sum of O) =1: 0.05-1; molar ratio of Zn (NO) 3 ) 2 ·6H 2 O：Ni(NO 3 ) 2 ·6H 2 O=1：0.05~1；
2) Preparation of bamboo-like Ni-N-C nano tube
Grinding the dodecahedron monocrystal ZIF-ZnNi and metal nickel salt obtained in the last step for 10-60 min, then placing the ground dodecahedron monocrystal ZIF-ZnNi and metal nickel salt into a quartz boat, and placing the quartz boat into a tube furnace for 2-5 min o C min -1 Raising the temperature from room temperature to 800-1100 DEG C o C, keeping for 1-3 h, and naturally cooling to room temperature;
wherein, the amount of metal nickel salt corresponding to each 1. 1g single crystal ZIF-ZnNi is 0.2-4 g;
3) Bamboo-like Ni-N-C nanotube surface coated polyion liquid
Dropwise adding an ethanol mixed solution containing a functionalized ionic liquid monomer, a cross-linking agent and azodiisobutyronitrile into the prepared bamboo-like Ni-N-C, and then carrying out 70-80 o C reacting for 12-24 h, and then reacting for 90-100 h o C, reacting for 10-24 hours; the bamboo-shaped Ni-N-C@ polyion liquid can be obtained;
wherein, each 1. 1g bamboo-like Ni-N-C corresponding mixed solution is 0.1-15 g; the mass ratio of the mixed solution is that the functionalized ionic liquid monomer: crosslinking agent: azobisisobutyronitrile: ethanol=0.1 to 2:0.1: 0.005-0.05: 0.5-3;
4) Super-crosslinking mesoporous preparation method of polyion liquid
Adding the prepared bamboo-like Ni-N-C@ polyion liquid into 1, 2-dichloroethane for 40-60 percent o C soaking for 1-4 h, then adding anhydrous ferric trichloride, and heating to 80-100 o C, reacting for 10-24 hours, washing with ethanol after the reaction is finished, centrifugally separating, and drying to obtain the bamboo-like Ni-N-C@ mesoporous polyion liquid;
wherein, 5-20 g of 1, 2-dichloroethane and 0.1-0.3 g of anhydrous ferric trichloride are added into each 0.1-g bamboo-like Ni-N-C nanotube surface coated polyion liquid.
2. The method for preparing a bamboo-like core-shell photo-thermal catalyst according to claim 1, wherein the metal nickel salt is Ni (NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 、NiSO 4 、NiCl 2 ·6H 2 O、NiCl 2 Nickel acetate tetrahydrate (C) 4 H 14 NiO 8 ）、Ni(CH 3 COO) 2 Nickel phosphate, nickel dihydrogen phosphate, basic nickel carbonate, nickel sulfamate or nickel bromide.
3. The method for preparing the bamboo-like core-shell photo-thermal catalyst according to claim 1, wherein the cross-linking agent is divinylbenzene or 4-chloromethylstyrene.
4. The method for preparing the bamboo-like core-shell photo-thermal catalyst according to claim 1, wherein the functionalized ionic liquid-containing monomer is 1-propylsulfo-3-vinylimidazolium bisulfate, 1- (3 ' -carboxypropyl) -3-vinylimidazolium bromide, 1- (2 ' -aminoethyl) -3-vinylimidazolium bromide, 1-ethyl-3-vinylimidazolium bromide, 1- (2 ' -hydroxyethyl) -3-vinylimidazolium bromide, ethyldiphenyl (4-vinylphenyl) phosphonium bromide, 1- (3 ' -carboxypropyl) -3-vinylimidazolium iodide, 1- (2 ' -aminoethyl) -3-vinylimidazolium iodide, 1-ethyl-3-vinylimidazolium iodide, 1- (2 ' -hydroxyethyl) -3-vinylimidazolium iodide, 1- (3 ' -carboxypropyl) -3-vinylimidazolium chloride, 1- (2 ' -aminoethyl) -3-vinylimidazolium chloride, 1-ethyl-3-vinylimidazolium chloride or 1- (2 ' -hydroxyethyl) -3-vinylimidazolium chloride.
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