CN115624976A - Preparation method and application of mosaic type zirconium oxide/cobalt oxide composite nano-particles - Google Patents
Preparation method and application of mosaic type zirconium oxide/cobalt oxide composite nano-particles Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000428 cobalt oxide Inorganic materials 0.000 title description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 title description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 49
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013207 UiO-66 Substances 0.000 claims abstract description 23
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 9
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000004809 Teflon Substances 0.000 claims description 10
- 229920006362 Teflon® Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000011278 co-treatment Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009210 therapy by ultrasound 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B32/40—Carbon monoxide
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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Abstract
The invention discloses an embedded ZrO 2 /Co 3 O 4 A preparation method of composite nano particles belongs to the technical field of nano materials, and comprises the steps of firstly, taking zirconium chloride and terephthalic acid as raw materials, and obtaining UIO-66 through solvothermal reaction; the UIO-66 thus obtained was then reacted with cetyltrimethylammonium bromide, cobalt chloride hexahydrate and 2-methylMixing imidazole, and carrying out secondary solvothermal reaction to obtain UIO-66/ZIF-67; and calcining the UIO-66/ZIF-67 in air to obtain the mosaic ZrO 2 /Co 3 O 4 Composite nanoparticles. In the composite nano-particles obtained by the invention, zrO 2 And Co 3 O 4 The nano particles are embedded with each other to make Co 3 O 4 The dispersity is obviously improved, the particle size is reduced, the carrier transmission distance can be shortened, and the photocatalysis of CO is promoted 2 Reducing, thereby having good environmental benefit.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to an embedded ZrO 2 /Co 3 O 4 Composite nanoparticles and their use in photocatalytic CO 2 Application in reduction.
Background
The huge consumption of fossil energy releases a large amount of CO 2 Gas, make CO in the atmosphere 2 The concentration increases day by day. The International Committee for climate Change (IPCC) projected CO in the atmosphere for 2100 years 2 The concentration will reach 590 ppm, which is 211% of the pre-industrial level, and the global temperature will rise by 1.5 ℃ on average, causing huge changes in global climate, resulting in serious ecological imbalance. In order to slow down the energy crisis and improve the global carbon cycle, CO is introduced by a photocatalysis technology 2 Conversion to solar fuels that can be stored, such as carbon monoxide (CO), methane (CH) 4 ) Formic acid (HCOOH), formaldehyde (CH) 2 O) and methanol (CH) 3 OH), etc., is a green, sustainable strategy.
Tricobalt tetraoxide (Co) 3 O 4 ) To CO 2 Has strong adsorption and activation effects, and is ideal CO 2 The catalyst is reduced. Reduction of Co 3 O 4 The catalyst has a size (e.g., nanoparticles) that exposes rich active sites and enhances CO 2 Molecular adsorption, and promotion of charge transfer. However, nanoparticles are extremely prone to agglomeration, thereby impairing their catalytic performance. How to inhibit the agglomeration of the nano particles and improve the dispersibility of the nano particles so as to improve the photocatalytic CO 2 The reduction performance is a key problem to be solved.
Disclosure of Invention
The invention aims to provide inlaid ZrO aiming at the defects in the existing nano particle preparation 2 /Co 3 O 4 Preparation method of composite nano-particles, which uses UIO-66/ZIF-67 composite metal organic framework as precursor and constructs inlaid ZrO by calcination method 2 /Co 3 O 4 The composite nano-particles have good visible light catalytic activity, so that good environmental benefits can be exerted.
In order to realize the purpose, the invention adopts the following technical scheme:
embedded ZrO 2 /Co 3 O 4 The composite nano-particles are prepared by firstly using zirconium chloride and terephthalic acid as raw materials and obtaining UIO-66 through solvothermal reaction; then mixing the obtained UIO-66 with hexadecyl trimethyl ammonium bromide, cobalt chloride hexahydrate and 2-methylimidazole, and carrying out secondary solvothermal reaction to obtain UIO-66/ZIF-67; then calcining the obtained UIO-66/ZIF-67 in air to obtain the mosaic ZrO 2 /Co 3 O 4 Composite nanoparticles.
The mosaic type ZrO 2 /Co 3 O 4 The preparation method of the composite nano-particles specifically comprises the following steps:
(1) Weighing 0.25-0.3 g of zirconium chloride, 0.18-0.2 g of terephthalic acid and 8-12 mL of acetic acid, magnetically stirring and dissolving in 40-50 mL of dimethylformamide until the solution is clear, then placing the obtained solution in a Teflon reaction kettle, reacting for 24 hours at 120 ℃, then cooling along with a furnace, and obtaining white powder through centrifugal separation, washing and drying;
(2) Adding 180-200 mg of the white powder obtained in the step (1), 5-8 mg of hexadecyl trimethyl ammonium bromide and 380-400 mg of cobalt chloride hexahydrate into 40-50 mL of methanol, adding 1790-1800 mg of 2-methylimidazole after ultrasonic-magnetic stirring, placing the mixed solution into a Teflon reaction kettle, reacting for 12 hours at 90 ℃, then cooling along with a furnace, and obtaining purple powder through centrifugal separation, washing and drying;
(3) Placing the purple powder obtained in the step (2) into a muffle furnace for calciningObtaining a black powder, i.e. the mosaic type ZrO 2 /Co 3 O 4 Composite nanoparticles.
Further, the time of the magnetic stirring in the step (1) is controlled to be 30 minutes; the rotation speed of the centrifugal separation is 9000 rpm, and the time is 3 minutes; the washing is carried out for three times by using dimethylformamide and methanol respectively; the drying is specifically vacuum drying at 60 ℃ for 12 hours.
Further, the ultrasonic-magnetic stirring in the step (2) is that the ultrasonic is firstly carried out for 20 minutes, and then the magnetic stirring is carried out for 5 to 10 minutes at 500 rpm; the rotation speed of the centrifugal separation is 9000 rpm, and the time is 3 minutes; the washing is carried out for three times by using methanol and one time by using deionized water; the drying is specifically vacuum freeze drying for 12 hours.
Further, in the step (3), the temperature rise rate of the muffle furnace is 2 ℃/min, the calcining temperature is 600-700 ℃, and the time is 1-5 hours.
The thus-obtained inlaid ZrO 2 /Co 3 O 4 In the composite nano-particles, zrO 2 And Co 3 O 4 Nanoparticles are embedded into each other to make Co 3 O 4 The dispersibility is obviously improved, the particle size is reduced, and the carrier transmission distance can be shortened, so that the photocatalyst has good photocatalytic activity and can be used for photocatalysis of CO 2 And (4) reducing.
The invention innovatively provides that UIO-66/ZIF-67 composite metal organic framework is used as a precursor, and UIO-66 is converted into TiO in the high-temperature calcination process 2 Nanoparticles, ZIF-67 conversion to Co 3 O 4 Nano particles are uniformly embedded in TiO 2 Between the nanoparticles so that Co is present 3 O 4 The dispersibility of (2) is improved; at the same time due to TiO 2 Presence of nanoparticles, co 3 O 4 The growth of the nanoparticles is inhibited and the particle size is reduced. Compared with Co obtained by direct calcination of ZIF-67 3 O 4 Nanoparticles of the mosaic type ZrO 2 /Co 3 O 4 The photocatalytic performance of the composite nano-particles is greatly improved.
The invention has the beneficial effects that:
(1) The invention creatively uses UIO-66/ZIF-67 composite metal organic framework as a precursor, and builds the mosaic ZrO by high-temperature calcination 2 /Co 3 O 4 The composite nano-particles provide a new idea for the technical field of nano-materials.
(2) Mosaic ZrO prepared by the invention 2 /Co 3 O 4 The composite nano-particles have good dispersibility and small particle size, and overcome Co 3 O 4 The catalyst is easy to agglomerate, and the charge transfer is greatly promoted, so that the photocatalytic CO is improved 2 Reduction performance, to solve the problem of application of nano-catalyst to CO 2 The key scientific problem of restoration provides a solution strategy.
(3) In the preparation method provided by the invention, the raw materials are easy to obtain, the price is low, the instruments and equipment are simple, the process operation is simple, and good environmental benefits are achieved.
Drawings
FIG. 1 is an X-ray diffraction pattern of nanoparticles prepared in examples and comparative examples 1 to 3;
FIG. 2 is a scanning electron microscope image of nanoparticles prepared in examples and comparative examples 1 to 3;
FIG. 3 shows the inlaid ZrO produced in example 2 /Co 3 O 4 An elemental profile of the composite nanoparticle;
FIG. 4 is a graph comparing photocurrent and electrochemical impedance of nanoparticles prepared in examples and comparative examples 1 to 3;
FIG. 5 is photocatalytic CO of nanoparticles prepared in examples and comparative examples 1 to 3 2 Performance is compared to the graph.
Detailed Description
Embedded ZrO 2 /Co 3 O 4 The preparation method of the composite nano-particles specifically comprises the following steps:
(1) Weighing 0.25-0.3 g of zirconium chloride, 0.18-0.2 g of terephthalic acid and 8-12 mL of acetic acid, magnetically stirring in 40-50 mL of dimethylformamide for 30 minutes to dissolve the zirconium chloride and the terephthalic acid until the zirconium chloride and the acetic acid are clear, then placing the obtained solution in a 100 mL Teflon reaction kettle, reacting at 120 ℃ for 24 hours, cooling along with a furnace, centrifugally separating at 9000 rpm for 3 minutes, washing dimethylformamide and methanol for three times respectively, and drying in vacuum at 60 ℃ for 12 hours to obtain white powder;
(2) Adding 180-200 mg of the white powder obtained in the step (1), 5-8 mg of hexadecyl trimethyl ammonium bromide and 380-400 mg of cobalt chloride hexahydrate into 40-50 mL of methanol together, performing ultrasonic stirring at 500rpm for 20 minutes, performing magnetic stirring for 5-10 minutes, then adding 1790-1800 mg of 2-methylimidazole, placing the mixed solution into a 100 mL Teflon reaction kettle, reacting at 90 ℃ for 12 hours, then cooling along with a furnace, performing centrifugal separation at 9000 rpm for 3 minutes, washing with methanol for three times, washing with deionized water for one time, and performing vacuum freeze drying for 12 hours to obtain purple powder;
(3) Placing the purple powder obtained in the step (2) into a muffle furnace, heating to 600-700 ℃ at the speed of 2 ℃/min, and calcining for 1-5 hours to obtain the mosaic ZrO 2 /Co 3 O 4 Black powder of composite nanoparticles.
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
(1) Weighing 280 mg of zirconium chloride, 200 mg of terephthalic acid and 10 mL of acetic acid, magnetically stirring in 43 mL of dimethylformamide for 30 minutes to dissolve the zirconium chloride, the terephthalic acid and the acetic acid until the zirconium chloride and the acetic acid are clear, then placing the obtained solution in a 100 mL Teflon reaction kettle, reacting at 120 ℃ for 24 hours, then cooling along with a furnace, centrifugally separating at 9000 rpm for 3 minutes, washing the dimethylformamide and the methanol respectively for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain white UIO-66 powder;
(2) Adding 200 mg of the white powder obtained in the step (1), 6 mg of hexadecyl trimethyl ammonium bromide and 380 mg of cobalt chloride hexahydrate into 46 mL of methanol, performing ultrasonic stirring for 20 minutes, magnetically stirring for 5 minutes at 500rpm, adding 1790 mg of 2-methylimidazole, placing the mixed solution into a 100 mL teflon reaction kettle, reacting for 12 hours at 90 ℃, cooling along with the furnace, performing centrifugal separation for 3 minutes at 9000 rpm, washing for three times with methanol, washing once with deionized water, and performing vacuum freeze drying for 12 hours to obtain UIO-66/ZIF-67 powder;
(3) The UIO-66/ZIF-67 powder obtained in the step (2) is placed in a muffle furnace, heated to 600 ℃ at the speed of 2 ℃/min and calcined for 2 hours to obtain black mosaic ZrO 2 /Co 3 O 4 Composite nanoparticles.
Comparative example 1
(1) Weighing 280 mg of zirconium chloride, 200 mg of terephthalic acid and 10 mL of acetic acid, magnetically stirring in 43 mL of dimethylformamide for 30 minutes to dissolve the zirconium chloride, the terephthalic acid and the acetic acid until the zirconium chloride and the acetic acid are clear, then placing the obtained solution in a 100 mL Teflon reaction kettle, reacting at 120 ℃ for 24 hours, then cooling along with a furnace, centrifugally separating at 9000 rpm for 3 minutes, washing the dimethylformamide and the methanol respectively for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain UIO-66 white powder;
(2) Putting the white powder obtained in the step (1) into a muffle furnace, heating to 600 ℃ at the speed of 2 ℃/min, and calcining for 2 hours to obtain white ZrO 2 And (3) nanoparticles.
Comparative example 2
(1) Adding 6 mg of hexadecyl trimethyl ammonium bromide and 380 mg of cobalt chloride hexahydrate into 46 mL of methanol together, performing ultrasonic treatment for 20 minutes, performing magnetic stirring for 5 minutes, adding 1790 mg of 2-methylimidazole, placing the mixed solution into a 100 mL Teflon reaction kettle, reacting for 12 hours at 90 ℃, cooling along with a furnace, performing centrifugal separation for 3 minutes at 9000 rpm, washing for three times with methanol, washing for one time with deionized water, and performing vacuum freeze drying for 12 hours to obtain ZIF-67 purple powder;
(2) Putting the purple powder obtained in the step (1) into a muffle furnace, heating to 600 ℃ at the speed of 2 ℃/min, and calcining for 2 hours to obtain black Co 3 O 4 And (3) nanoparticles.
Comparative example 3
(1) Fully mixing all ZIF-67 purple powder obtained in comparative example 2 with 200 mg of UIO-66 white powder obtained in comparative example 1 by grinding to obtain UIO-66+ ZIF-67 light purple powder;
(2) Putting the UIO-66+ ZIF-67 light purple powder obtained in the step (1) into a muffle furnace, heating to 600 ℃ at the speed of 2 ℃/min, and calcining for 2 hours to obtainBlack ZrO 2 +Co 3 O 4 And (3) nanoparticles.
FIG. 1 is an X-ray diffraction pattern of nanoparticles prepared in examples and comparative examples 1 to 3. As can be seen from the figure, the mosaic type ZrO 2 /Co 3 O 4 The composite nanoparticles also contain ZrO 2 And Co 3 O 4 Characteristic peak of (b), indicating ZrO 2 /Co 3 O 4 The composite nanoparticles were successfully prepared.
FIG. 2 is a scanning electron microscope image of nanoparticles prepared in examples and comparative examples 1 to 3. As is apparent from the figure, co 3 O 4 And ZrO 2 +Co 3 O 4 The agglomeration of the nano-particles is serious, the particle size is large, and the mosaic ZrO prepared in the example 2 /Co 3 O 4 The composite nano particles have smaller size and uniform particle size.
FIG. 3 shows the inlaid ZrO produced in example 2 /Co 3 O 4 Elemental distribution map of composite nanoparticles. The figure shows that the Zr and Co elements are uniformly distributed in the sample.
Performance testing
1. Comparative photo-current test chart and electrochemical impedance test of nano-particles prepared in examples and comparative examples
The photocurrent test was performed using a three-electrode quartz cell and a model CHI660E electrochemical workstation of shanghai chenhua instruments. Pt and Ag/AgCl were used as counter and reference electrodes. The working electrode was prepared by dispersing 2 mg of the sample in 0.5 mL of dimethylformamide, applying 20 μ L of the solution to the FTO at an application area of 0.25 square centimeters, and starting the test after the sample had dried. The electrolyte solution is prepared by dissolving 20 mg of ruthenium pyridine in a mixed solvent of 14 mL of deionized water, 14 mL of triethanolamine and 42 mL of acetonitrile.
Electrochemical impedance spectroscopy tests were performed using a three-electrode quartz cell and a ParstaTMC-type electrochemical workstation from Princeton, USA. Pt and Ag/AgCl were used as counter and reference electrodes. The working electrode was prepared by dispersing 2 mg of the sample in 0.5 mL of dimethylformamide, applying 20. Mu.L of the solution to FTO over a 0.25 square smear fieldCm, and the test is started after the sample is dried. The electrolyte solution is prepared by mixing 164.6 mg K 3 [Fe(CN) 6 ]、211.2 mg K 4 [Fe(CN) 6] 745.5 mg KCl dissolved in 100 mL deionized water.
Fig. 4 is a graph showing a comparison of photocurrent and electrochemical impedance of nanoparticles prepared in examples and comparative examples 1 to 3. As can be seen from FIG. 4, compared with single-phase ZrO 2 、Co 3 O 4 Or is ZrO 2 +Co 3 O 4 Of inlaid type ZrO 2 /Co 3 O 4 The composite nanoparticles all exhibit lower charge transfer resistance and more efficient electron transfer.
2. The nanoparticles prepared in the examples and comparative examples were subjected to photocatalytic CO 2 The reduction performance test comprises the following specific steps:
(1) 1 mg of nanoparticles and 8 mg of tris (2' 2-bipyridyl) ruthenium (II) chloride were taken and dispersed in a quartz glass reactor containing 1 mL of triethanolamine, 2 mL of deionized water and 3 mL of acetonitrile;
(2) Sealing the reactor, pumping out air from the reactor by vacuum pump, and introducing CO 2 Gas, bleed-vent was repeated three times to ensure that the reactor was filled with CO 2 A gas;
(3) Placing the reactor under a 300W xenon lamp (provided with a 420 nm filter) for illumination, keeping the temperature constant (30 ℃) and stirring;
(4) At regular intervals, reactor gas was withdrawn using a sampling needle and quantitatively analyzed using gas chromatography.
FIG. 5 is a graph showing photocatalytic CO of nanoparticles prepared in examples and comparative examples 1 to 3 2 Performance is compared to the graph. The results show that the inlaid ZrO prepared in the examples 2 /Co 3 O 4 The catalytic property of the composite nanoparticles is ZrO 2 5.1 times of the nano-particles, is Co 3 O 4 1.7 times of the nano-particles is ZrO 2 +Co 3 O 4 1.2 times of the composite nano-particles show that the composite nano-particles obtained by the invention have excellent catalytic effect.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. Embedded ZrO 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: firstly, zirconium chloride and terephthalic acid are taken as raw materials, and UIO-66 is obtained through solvothermal reaction; then mixing the obtained UIO-66 with hexadecyl trimethyl ammonium bromide, cobalt chloride hexahydrate and 2-methylimidazole, and carrying out secondary solvothermal reaction to obtain UIO-66/ZIF-67; and calcining the UIO-66/ZIF-67 in air to obtain the mosaic ZrO 2 /Co 3 O 4 Composite nanoparticles.
2. A mosaic ZrO according to claim 1 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: the method comprises the following steps:
(1) Weighing a proper amount of zirconium chloride, terephthalic acid and acetic acid, magnetically stirring and dissolving in dimethylformamide until the solution is clear, then placing the obtained solution in a Teflon reaction kettle, reacting for 24 hours at 120 ℃, then cooling along with a furnace, and obtaining white powder through centrifugal separation, washing and drying;
(2) Adding the white powder obtained in the step (1), cetyl trimethyl ammonium bromide and cobalt chloride hexahydrate into methanol, adding a proper amount of 2-methylimidazole after ultrasonic-magnetic stirring, placing the mixed solution into a Teflon reaction kettle, reacting for 12 hours at 90 ℃, then cooling along with a furnace, and obtaining purple powder through centrifugal separation, washing and drying;
(3) Calcining the purple powder obtained in the step (2) in a muffle furnace to obtain black powder, namely the inlaid ZrO 2 /Co 3 O 4 Composite nanoparticles.
3. A mosaic ZrO according to claim 2 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: the amount of zirconium chloride used in step (1) is 0.25-0.3 g, 0.18-0.2 g of terephthalic acid, 8-12 mL of acetic acid and 40-50 mL of dimethylformamide.
4. The inlaid type ZrO of claim 2 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: the washing in the step (1) is carried out for three times by respectively using dimethylformamide and methanol; the drying is specifically vacuum drying at 60 ℃ for 12 hours.
5. The inlaid type ZrO of claim 2 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: in the step (2), the dosage of the white powder is 180-200 mg, the dosage of the hexadecyl trimethyl ammonium bromide is 5-8 mg, the dosage of the cobalt chloride hexahydrate is 380-400 mg, the dosage of the methanol is 40-50 mL, and the dosage of the 2-methylimidazole is 1790-1800 mg.
6. The inlaid type ZrO of claim 2 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: in the step (2), the ultrasonic-magnetic stirring is performed for 20 minutes by ultrasonic and then for 5-10 minutes by magnetic stirring; the washing is carried out for three times by using methanol and one time by using deionized water; the drying is specifically vacuum freeze drying for 12 hours.
7. The inlaid type ZrO of claim 2 2 /Co 3 O 4 The preparation method of the composite nano-particles is characterized by comprising the following steps: in the step (3), the temperature rise rate of the muffle furnace is 2 ℃/min, the calcining temperature is 600-700 ℃, and the time is 1-5 hours.
8. A mosaic ZrO prepared by the process as claimed in any of claims 1 to 7 2 /Co 3 O 4 Composite nanoparticles.
9. A process as claimed in claim 8Of the inlaid type ZrO 2 /Co 3 O 4 Photocatalytic CO treatment by composite nano-particles 2 Application in reduction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116173960A (en) * | 2023-03-09 | 2023-05-30 | 福州大学 | Preparation method and application of zirconia/cobalt/carbon composite catalyst |
| CN116747885A (en) * | 2023-06-06 | 2023-09-15 | 常州大学 | ZIF-67-derived CsPbBr 3 /Co 3 O 4 Preparation method and application of composite photocatalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159130A (en) * | 2017-05-22 | 2017-09-15 | 山东大学 | A kind of preparation method of metal organic framework tunica fibrosa |
| US20190168173A1 (en) * | 2017-10-27 | 2019-06-06 | Regents Of The University Of Minnesota | Nanocomposite membranes and methods of forming the same |
| CN112517010A (en) * | 2020-11-27 | 2021-03-19 | 华南理工大学 | Metal/ZrO produced by thermal stress stretching strategy2Multi-stage framework material and preparation method thereof |
| CN113307990A (en) * | 2021-06-09 | 2021-08-27 | 上海科技大学 | Composite material and preparation method and application thereof |
-
2022
- 2022-11-28 CN CN202211498153.4A patent/CN115624976B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159130A (en) * | 2017-05-22 | 2017-09-15 | 山东大学 | A kind of preparation method of metal organic framework tunica fibrosa |
| US20190168173A1 (en) * | 2017-10-27 | 2019-06-06 | Regents Of The University Of Minnesota | Nanocomposite membranes and methods of forming the same |
| CN112517010A (en) * | 2020-11-27 | 2021-03-19 | 华南理工大学 | Metal/ZrO produced by thermal stress stretching strategy2Multi-stage framework material and preparation method thereof |
| CN113307990A (en) * | 2021-06-09 | 2021-08-27 | 上海科技大学 | Composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 谭海燕;石新雨;王权;林武;谭学才;: "(111)晶面暴露的NiO纳米催化剂的制备及其CO催化氧化性能", 华中农业大学学报, no. 04 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116173960A (en) * | 2023-03-09 | 2023-05-30 | 福州大学 | Preparation method and application of zirconia/cobalt/carbon composite catalyst |
| CN116747885A (en) * | 2023-06-06 | 2023-09-15 | 常州大学 | ZIF-67-derived CsPbBr 3 /Co 3 O 4 Preparation method and application of composite photocatalyst |
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