CN114471730B - NH2-MIL-101 (Fe) @ SNW-1 composite catalyst and preparation method and application thereof - Google Patents
NH2-MIL-101 (Fe) @ SNW-1 composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000013177 MIL-101 Substances 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000013310 covalent-organic framework Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
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- 239000012621 metal-organic framework Substances 0.000 description 3
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- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- 239000011941 photocatalyst Substances 0.000 description 2
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- 238000002791 soaking Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion 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
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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]
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The invention discloses an NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst, a preparation method and application thereof, wherein SNW-1 in the composite catalyst is connected to the surface of NH 2 -MIL-101 (Fe) through an amide bond, and the preparation method comprises the following steps: synthesizing NH 2 -MIL-101 (Fe), carrying out aldehyde modification on amino on the surface of the NH 2 -MIL-101 (Fe), mixing the NH 2 -MIL-101 with terephthalaldehyde and melamine, and carrying out hydrothermal reaction to obtain a target catalyst; the method is simple, low in cost, high in stability of the obtained composite catalyst, strong in capability of decomposing water into hydrogen by photocatalysis, and has application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a composite catalyst composed of an NH 2 -MIL-101 (Fe) nanomaterial and a covalent organic framework material SNW-1, a preparation method thereof and application thereof in the field of photocatalysis.
Background
With the increasing attention of people to global energy crisis and environmental pollution, photodecomposition of aquatic hydrogen is a very active field of energy research, and is the most promising strategy for obtaining alternative energy, so that development of an effective photocatalyst for photodecomposition of aquatic hydrogen is of great importance. Covalent Organic Frameworks (COFs) and Metal Organic Frameworks (MOFs) are crystalline and porous materials assembled from pure organic molecules or with metal ions (metal clusters) through covalent or coordination bonds, and have been used in various fields such as gas storage, catalysis and sensing. Recently, COFs have become a novel photocatalytic material for photocatalytic hydrogen production due to its ordered porous structure, large surface area and adjustable band gap. Furthermore, COFs generally exhibit excellent chemical stability, especially in imine-linked nitrogen-containing COFs, since they are composed entirely of covalent bonds. To date, most reported COFs are 2D structures with strong interactions between adjacent layers. p-p stacking mediates electronic interactions between layers and thus provides another possible route for charge carrier transport in addition to transfer within covalent layers. Furthermore, most COFs, especially those based on schiff bases, generally exhibit orange to dark red colors due to the absorbance of the groups and the larger conjugated system, making them better in the visible region of light response.
So far, there are few reports of Guan Erwei COFs decomposing hydrogen, and the hydrogen production rate is as high as 1.9 mmol.g -1·h-1. But the hydrogen generation rate is far from expected and is not as good as conventional semiconductor photocatalysts such as metal oxides and sulfides. The strong recombination rate of photo-generated electron-hole pairs of COFs is an important reason for limiting its hydrogen production rate. Developing a suitable semiconductor composite to ensure reverse migration of electrons and holes through Conduction Band (CB) and Valence Band (VB) shifts is an effective strategy to improve charge-carrier separation.
Due to the nature of the defined pore structure, COFs can be subjected to a range of functional modifications on its surface and can also serve as an excellent matrix for supporting metal nanoparticles or other species. Thus, some COFs-supported gold, palladium and CdS hybrid materials were prepared by researchers and studied for their catalytic activity. However, most of these studies have focused mainly on combinations of two different species, the interactions between which are weak, while covalent linkages between the parent components are very limited in the reported literature.
Disclosure of Invention
In order to solve the problems of low photocatalytic activity and easiness in recombination of photo-generated carriers of a single COFs material, the invention provides a composite material composed of NH 2 -MIL-101 (Fe) and SNW-1, which are connected through covalent bonds, so that photo-generated electrons between the NH 2 -MIL-101 (Fe) and the SNW-1 are more favorably transferred, and the catalytic hydrogen production performance of the composite catalyst is high.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
The invention provides a NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst, wherein NH 2 -MIL-101 (Fe) nano Materials (MOFs) and SNW-1 (COFs prepared from terephthalaldehyde and melamine) are connected through an amide bond.
Preferably, in the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst, the mass ratio of NH 2 -MIL-101 (Fe) to SNW-1 is 1:0.4-1.
The invention also provides a method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst, which specifically comprises the following steps: NH 2 -MIL-101 (Fe) nano material is synthesized by a hydrothermal method, then aldehyde modification is carried out on the surface of the nano material, and then SNW-1 is assembled on the surface of the nano material by the hydrothermal method.
Preferably, the method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst comprises the following specific steps:
s1, taking DMF as a solvent, adding 2-amino terephthalic acid and FeCl 3·6H2 O, uniformly mixing, and performing hydrothermal reaction to obtain a first precursor;
S2, dispersing the first precursor in ethanol, adding terephthalaldehyde and 1, 2-dichlorobenzene, vacuumizing, and performing hydrothermal reaction to obtain a second precursor;
S3, adding the second precursor, terephthalaldehyde and melamine into a solvent by taking the mixed solution of 1, 2-dichlorobenzene and ethanol as the solvent, uniformly mixing, vacuumizing, and performing hydrothermal reaction to obtain the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst.
More preferably, the molar ratio of 2-amino terephthalic acid to FeCl 3·6H2 O in step S1 is 1:1.8-2.2.
More preferably, the molar ratio of the first precursor to terephthalaldehyde in the step S2 is 1:1.5-2.2.
More preferably, the molar ratio of the second precursor to terephthalaldehyde and melamine in the step S3 is 1:1-4:1-4.
More preferably, the hydrothermal reaction in step S2 is performed at a temperature of 80 to 120 ℃ for a reaction time of 12 to 24 hours.
More preferably, the hydrothermal reaction in step S3 is performed at a temperature of 100 to 150 ℃ for a reaction time of 8 to 12 hours.
The invention also provides application of the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst in preparing hydrogen by photocatalytic pyrolysis, which has strong hydrogen production capacity and high stability and can be recycled.
The beneficial effects of the invention are as follows: compared with NH 2 -MIL-101 (Fe) and SNW-1, the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst provided by the invention has larger specific surface area and obviously enhanced light absorption capacity; and because NH 2 -MIL-101 (Fe) and SNW-1 are connected through generating a new chemical bond (an amide bond), a migration channel is provided for a photo-generated carrier, a Z-type heterojunction is formed, the photo-generated electron-hole recombination rate is greatly reduced, and the performance of photo-catalytic cracking of water to produce hydrogen is obviously improved. In addition, the composite catalyst prepared by the invention has high stability, mainly characterized in that NH 2 -MIL-101 (Fe) and SNW-1 are bridged by amide bonds instead of Van der Waals force interaction, thus the secondary pollution of water body is avoided, and the preparation process is simple, easy to operate and low in production cost, so that the composite catalyst has great potential in practical application.
Drawings
FIG. 1 is an SEM image of a composite catalyst prepared according to example 1 of the present invention;
FIG. 2 is a diagram showing the elemental distribution of the composite catalyst prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the composite catalyst prepared in example 1 of the present invention;
FIG. 4 is a graph showing the light absorption characteristics of the composite catalyst prepared in example 1 of the present invention;
FIG. 5 is an XPS spectrum of the composite catalyst prepared in example 1 of the present invention;
FIG. 6 is a graph showing the photocatalytic water splitting hydrogen production performance of the composite catalyst prepared in example 1 of the present invention;
FIG. 7 is a graph showing the recycling of hydrogen production performance of the composite catalyst prepared in example 1 according to the present invention.
Detailed Description
The present invention will be further described with reference to the drawings and examples, which are only for more clearly illustrating the technical solution of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1
The preparation method of the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst comprises the following steps:
(1) 224.6mg of NH 2-H2 BDC (2-amino terephthalic acid, 1.24 mmol) and 675mg of FeCl 3·6H2 O (2.5 mmol) were added to a 100mL glass liner containing 15mL DMF (N, N-dimethylformamide) and sonicated until the solid was completely dissolved. Then put into a hydrothermal kettle, the temperature is raised to 110 ℃, and the temperature is naturally reduced after 12 hours of heat preservation. Centrifuging at 8,000rpm for 10 min, collecting brown black powder, soaking in DMF for 2 hr, soaking in ethanol for 4 hr, and drying in vacuum oven to obtain first precursor NH 2 -MIL-101 (Fe).
(2) 400Mg of the first precursor was weighed into a 60mL jar, added with 20mL of ethanol for ultrasonic dispersion, then added with 400mg of terephthalaldehyde (2.98 mmol), 40mL of a mixed solution of 1, 2-dichlorobenzene and ethanol (v: v=4:1), and added with 2mL of 3mol/L acetic acid solution after 5 minutes of ultrasonic treatment. The jar was sealed with a plug of silica gel, air was drawn after low temperature freezing, then high purity nitrogen was again charged for a total of 6 cycles, and no gas was charged after the last vacuum (vacuum was applied to prevent the terephthalaldehyde from polymerizing on itself). Then put into a hydrothermal kettle, the temperature is increased to 85 ℃, the temperature is kept for 16 hours, and after natural cooling, the brown product is obtained by centrifugation with a centrifuge. The product was washed with hot ethanol several times and dried at low temperature to give a second precursor, designated NH 2 -MIL-101 (Fe) (CHO).
(3) An amount of the second precursor, 150mg terephthalaldehyde, 172mg melamine and 40mL1, 2-dichlorobenzene/ethanol (4:1=v: v) was added to a 60mL wide-mouth bottle, and after 5 minutes of sonication, 3-M acetic acid (0.8 mL) was added. And then sealing the wide-mouth bottle by using a silica gel plug, circulating for 6 times after low-temperature freezing, vacuumizing and filling nitrogen, finally keeping a vacuum state, putting into an autoclave, heating to 110 ℃ and preserving heat for 12 hours. It was collected by centrifugation at 8,000rpm for 10 minutes, then washed with absolute ethanol, and dried in vacuo to give a brown powder, which was designated as a composite catalyst, MS-1.
In the embodiment, the 1, 2-dichlorobenzene and ethanol are used as the mixed solvent, so that the dissolution can be promoted, and the smooth reaction can be promoted. Acetic acid is used as a catalyst for promoting the dehydration condensation reaction of the amino groups on the surface of the first precursor in the step (2) and terephthalaldehyde, and the condensation reaction of the aldehyde groups on the surface of the second precursor in the step (3) and the amino groups in melamine.
Changing the addition amount of the second precursor in the step (3) to prepare the composite catalysts with different SNW-1 loading amounts, wherein the composite catalysts are respectively expressed as MS-1-0.4, MS-1-0.8 and MS-1-1.0. Wherein 0.4, 0.6, 0.8 and 1.0 respectively refer to the ratio of NH 2 -MIL-101 (Fe) mass to SNW-1 mass in the composite material being 1:0.4, 1:0.6, 1:0.8 and 1:1, respectively, and if the loading amounts are expressed in percentage, the loading amounts are 29%, 38%, 44% and 50% (the loading amount calculation method is SNW-1 mass/total mass of the composite material multiplied by 100%).
Comparative example 1
The preparation of pure NH 2 -MIL-101 (Fe) nanomaterial was the same as in step (1) of example 1.
Comparative example 2
The preparation of the pure covalent organic framework material SNW-1 comprises the following steps:
300mg of terephthalaldehyde, 344mg of melamine and 50mL of 1, 2-dichlorobenzene/ethanol (4:1=v: v) were added to a 60mL jar, and after 5 minutes of ultrasonic treatment, 3-M acetic acid (0.8 mL) was added. And then sealing the wide-mouth bottle by using a silica gel plug, circulating for 6 times after low-temperature freezing, vacuumizing and filling nitrogen, finally keeping a vacuum state, putting into an autoclave, heating to 110 ℃ and preserving heat for 12 hours. It was collected by centrifugation at 8,000rpm for 10 minutes, and then washed with absolute ethanol, and dried in vacuo to give SNW-1 as a white powder.
The materials prepared in example 1 and comparative example were subjected to various characterizations, and the superiority of the composite catalyst prepared in the present invention was determined by comparative analysis of the results. Specific characterization and analysis results are as follows:
① Characterization of topography
The morphology of the composite catalysts prepared in example 1 and comparative examples 1-2, and NH 2 -MIL-101 (Fe) and SNW-1 were characterized, and the results are shown in FIGS. 1-2.
FIG. 1 shows SEM spectra of NH 2 -MIL-101 (Fe), SNW-1 and MS-1-0.8, as can be seen from the figures: NH 2 -MIL-101 (Fe) synthesized by a hydrothermal method has a relatively uniform size (shown in a graph a); SNW-1 is spherical but not uniform in size (shown in panel b), possibly due to different degrees of polymerization; interestingly, it is apparent from the c and d plots that SNW-1 had a hollow spherical structure on the surface of NH 2 -MIL-101 (Fe) when assembled stepwise.
FIG. 2 is a SEM element distribution diagram of MS-1-0.8, in which the main elements O, fe and N are uniformly distributed on the shell-core material, indicating that SNW-1 has been successfully assembled on the surface of NH 2 -MIL-101 (Fe) in steps.
② Characterization of crystalline phases
The crystal structure and phase composition of each product in examples and comparative examples were analyzed by PXRD diffractometry, and the results are shown in fig. 3: the positions of the diffraction peaks of NH 2 -MIL-101 (Fe) appear at about 5 DEG, 9 DEG and 13 DEG, and a broader characteristic peak appears at 23.8 DEG for SNW-1, which is probably due to the microporous polymer itself and the poor crystal form, which is also the cause of the shift of part of the characteristic peaks of NH 2 -MIL-101 (Fe) in the MS-1-0.8 composite catalyst.
③ Characterization of light absorption Properties
The light absorption properties of each of the products in the examples and comparative examples were characterized by UV-vis DRS spectroscopy as shown in fig. 4: SNW-1 has light absorption capacity only at about 250nm, so that the SNW-1 can be excited only under ultraviolet irradiation, and NH 2 -MIL-101 (Fe) and MS-1-0.8 have strong light absorption capacity at 480 nm.
④ Chemical valence detection of elements in a sample
The chemical valence states of the main elements in each product were studied by X-ray photoelectron spectroscopy (XPS), and the XPS spectra of C1s, N1 s and Fe 2p between MS-1-0.8 and pure SNW-1, NH 2 -MIL-101 (Fe) samples were compared, and the results are shown in FIG. 5.
The full spectrum scanning spectrum is shown as a graph, NH 2 -MIL-101 (Fe) mainly comprises four elements of C, N, O and Fe, and SNW-1 comprises two elements of C and N, so that a small amount of O element is generated due to interference of a background. Most importantly, the d graph shows a fine spectrum of Fe 2p, and an NH 2 -MIL-101 (Fe) sample has two obvious peaks at the binding energies of 711.7eV and 726.0eV, which belong to Fe 2p 3/2 and Fe 2p 1/2 respectively, and in addition, a satellite peak at the binding energy of 716.5eV also belongs to Fe (III); the binding energies of MS-1-0.8 relative to Fe 2p 3/2 and Fe 2p 1/2 of NH 2 -MIL-101 (Fe) were reduced by 0.2eV and 0.8eV, respectively, which fully demonstrates that the N atom in SNW-1 coordinates with the Fe ion in NH 2 -MIL-101 (Fe).
Example 2
The photocatalytic hydrogen production properties of the composite catalyst prepared in example 1 were examined.
(1) Photocatalytic hydrogen production capability detection
50Mg of each sample was weighed and placed in a 500mL quartz reactor, 100mL of water containing 50% methanol was added, and 5mL of H 2PtCl6 (Pt concentration: 0.1 mg/mL) was added as a precursor, and Pt was deposited on the catalyst surface by an in situ photo-deposition method. 15mL of TEOA was added as a sacrificial agent. The catalyst was uniformly dispersed in the solution by magnetic stirring for 10 minutes before light irradiation. The sealed system was purged with N 2 for 20 minutes to remove air as much as possible. Then irradiated using a 300W xenon lamp (PERFECT LIGHT, PLS-SXE300C, beijing). The gases in the reaction system were taken every 30 minutes and detected by a gas chromatograph (GC 9700, techcomp).
As a control, the same method as described above was used to examine the catalytic hydrogen production performance of pure NH 2 -MIL-101 (Fe) and SNW-1.
The photocatalytic hydrogen production and hydrogen production efficiency of the core-shell nanocomposite catalyst with different loadings under simulated sunlight are shown in fig. 6. As can be seen from the graph a, the photocatalytic hydrogen production activities of pure NH 2 -MIL-101 (Fe) and SNW-1 are very low, and the hydrogen production amounts within 4 hours are only 2726.63 and 1992.99 mu mol/g respectively. The shell-core composite catalyst shows higher photocatalytic hydrogen production activity, and the hydrogen production amounts of MS-1-0.4, MS-1-0.6, MS-1-0.8 and MS-1-1.0 in 4 hours are respectively up to 6669.88, 7082.45, 7798.25 and 6609.31 mu mol g -1, and the hydrogen production rates are 1667.47, 1770.61, 1949.56 and 1652.33 mu mol h -1g-1 respectively, wherein the highest hydrogen production activity is MS-1-0.8.
(2) Stability detection for photocatalytic hydrogen production
The circulation experiment of photocatalytic hydrogen production is consistent with the operation of the step (1), except that only MS-1-0.8 is selected for research, after each experiment is finished, the material is washed twice by ethanol, centrifugally separated, dried and then continuously enters the next circulation.
As shown in FIG. 7, the results of the MS-1-0.8 cycle hydrogen production experiment show that MS-1-0.8 can maintain high photocatalytic hydrogen production activity in four times of cycle hydrogen production, and four times of hydrogen production are 7898.85, 7704.67, 7556.51 and 7689.08 mu mol/g respectively. The results of the above circulation experiments show that the prepared shell-core composite catalyst MS-1-0.8 has better stability in the photocatalysis process and potential application value in the aspect of hydrogen production by photocatalysis.
Taken together, the improvement in photocatalytic activity of the composite catalyst compared to NH 2 -MIL-101 (Fe) and SNW-1 was attributed to the bridging between NH 2 -MIL-101 (Fe) and SNW-1 through amide bonds, rather than simple physical mixing. In addition, experiments prove that the preparation process parameters are adjusted within a small range given in the specification, and the catalytic performance of the product is not obviously affected.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (8)
1. A method for preparing an NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst, which is characterized by comprising the following steps:
S1, taking DMF as a solvent, adding 2-amino terephthalic acid and FeCl 3·6H2 O, uniformly mixing, and performing hydrothermal reaction to obtain a first precursor;
S2, dispersing the first precursor in ethanol, adding terephthalaldehyde and 1, 2-dichlorobenzene, vacuumizing, and performing hydrothermal reaction to obtain a second precursor;
S3, adding the second precursor, terephthalaldehyde and melamine into a solvent by taking the mixed solution of 1, 2-dichlorobenzene and ethanol as the solvent, uniformly mixing, vacuumizing, and performing hydrothermal reaction to obtain the product, namely the composite catalyst with the surface amide bond of NH 2 -MIL-101 (Fe) connected with SNW-1.
2. The method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst according to claim 1, wherein the molar ratio of the 2-amino terephthalic acid to the FeCl 3·6H2 O in the step S1 is 1:1.8-2.2.
3. The method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst according to claim 1, wherein the molar ratio of the first precursor to terephthalaldehyde in the step S2 is 1:1.5-2.2.
4. The method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst according to claim 1, wherein the molar ratio of the second precursor to terephthalaldehyde and melamine in the step S3 is 1:1-4:1-4.
5. The method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst according to claim 1, wherein the hydrothermal reaction in the step S2 is performed at a temperature of 80-120 ℃ for 12-24 hours.
6. The method for preparing the NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst according to claim 1, wherein the hydrothermal reaction temperature in the step S3 is 100-150 ℃ and the reaction time is 8-12 h.
7. The NH 2 -MIL-101 (Fe) @ SNW-1 composite catalyst prepared according to any one of claims 1-6.
8. The use of the NH 2 -MILs-101 (Fe) @ SNW-1 composite catalyst according to claim 7 in photocatalytic decomposition of aqueous hydrogen.
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| CN113842953A (en) * | 2021-10-11 | 2021-12-28 | 石家庄铁道大学 | NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst and preparation method thereof |
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