CN114471730A - 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 50
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 31
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 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
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- 238000003786 synthesis reaction Methods 0.000 abstract 1
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- 239000000463 material Substances 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
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- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent 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
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- 238000005406 washing 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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- 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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- 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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- 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
- 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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- 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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- 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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Abstract
The invention discloses NH2-MIL-101(Fe) @ SNW-1 composite catalyst, preparation method and application thereof, wherein SNW-1 in the composite catalyst is connected with NH through amido bond2-MIL-101(Fe) surface, prepared by: first synthesis of NH2MIL-101(Fe), performing aldehyde modification on amino on the surface of the Fe, mixing the Fe with terephthalaldehyde and melamine, and performing hydrothermal reaction to obtain a target catalyst; the method is simple and low in cost, and the obtained composite catalyst is high in stability and strong in capability of producing hydrogen by photocatalytic water decomposition, and has an application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst prepared from NH2-MIL-101(Fe) nano material and covalent organic framework material SNW-1, and a preparation method and application thereof in the field of photocatalysis.
Background
With the increasing concern of people on global energy crisis and environmental pollution problems, hydrogen production by photolysis is a very active field of energy research, and is the most promising strategy for obtaining alternative energy, so that the development of an effective photocatalyst for hydrogen production by photolysis 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) via covalent or coordinate bonds and have been used in various fields, such as gas storage, catalysis and sensing. Recently, COFs are a novel photocatalytic material due to the ordered porous structure, large surface area and adjustable band gap, and can be used for photocatalytic hydrogen production. Furthermore, because COFs are composed entirely of covalent bonds, they generally exhibit excellent chemical stability, particularly in imine-linked nitrogen-containing COFs. To date, most of the 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. In addition, most of the COFs, especially those based on schiff bases, generally exhibit an orange-red to dark-red color due to the light absorption property of the radicals and a large conjugated system, so that they have a good light response capability in the visible region.
So far, reports about hydrogen decomposition of two-dimensional COFs are still few, and the hydrogen production rate is as high as 1.9 mmol/g-1·h-1. However, the rate of hydrogen generation is far from expected and is not as good as conventional semiconductor photocatalysts such as metal oxides and sulfides. The strong recombination rate of the photogenerated electron-hole pairs of COFs is an important reason for limiting the hydrogen production rate. The development of suitable semiconductor composite materials to ensure the reverse transport of electrons and holes through Conduction Band (CB) and Valence Band (VB) shifts is an effective strategy to improve the charge-carrier separation.
Because of the nature of the defined pore structure of COFs, a series of functional modifications can be made on the surface of COFs, and the COFs can also serve as an excellent matrix for supporting metal nanoparticles or other species. Therefore, some researchers have prepared some gold, palladium and CdS hybrid materials loaded on COFs, and studied the catalytic activity of the materials. However, most of these studies have focused mainly on two different kinds of combinations, where the interaction between them is weak and the covalent linkage between the parent components is very limited in the reported literature.
Disclosure of Invention
In order to solve the problems that the single COFs material is low in photocatalytic activity and easy to recombine photon-generated carriers, the invention provides a composite material prepared from NH2The composite material consisting of MIL-101(Fe) and SNW-1 is connected with each other through a covalent bond, so that the photo-generated electron transfer between the MIL-101(Fe) and the SNW-1 is facilitated, 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 NH2MIL-101(Fe) @ SNW-1 composite catalyst in which NH is present2MIL-101(Fe) nanomaterials (MOFs) were linked to SNW-1 (COFs prepared from terephthalaldehyde and melamine) by amide bonds.
Preferably, the NH is2NH in-MIL-101 (Fe) @ SNW-1 composite catalyst2The mass ratio of MIL-101(Fe) to SNW-1 is 1: 0.4-1.
The invention also provides a method for preparing the NH2-MIL-101(Fe) @ SNW-1 composite catalyst, which comprises the following steps: firstly synthesizing NH by a hydrothermal method2And (2) carrying out aldehyde modification on the surface of the MIL-101(Fe) nano material, and then assembling SNW-1 on the surface of the nano material by a hydrothermal method.
Preferably, the preparation of NH2The method of the-MIL-101 (Fe) @ SNW-1 composite catalyst is as follows:
s1 adding 2-amino terephthalic acid and FeCl by taking DMF as solvent3·6H2O, performing hydrothermal reaction after uniformly mixing to obtain a first precursor;
s2, dispersing the first precursor in ethanol, adding terephthalaldehyde and 1, 2-dichlorobenzene, performing vacuum-pumping treatment, and performing hydrothermal reaction to obtain a second precursor;
s3, taking a mixed solution of 1, 2-dichlorobenzene and ethanol as a solvent, and mixing a second precursor and p-phenylene-bisAdding formaldehyde and melamine into a solvent, uniformly mixing, vacuumizing, and carrying out hydrothermal reaction to obtain NH2MIL-101(Fe) @ SNW-1 composite catalyst.
More preferably, the 2-aminoterephthalic acid and FeCl are reacted in step S13·6H2The molar ratio of O is 1: 1.8-2.2.
More preferably, the molar ratio of the first precursor to terephthalaldehyde in step S2 is 1: 1.5-2.2.
More preferably, the molar ratio of the second precursor to the terephthalaldehyde and the melamine in step S3 is 1: 1-4.
More preferably, the temperature of the hydrothermal reaction in step S2 is 80 to 120 ℃ and the reaction time is 12 to 24 hours.
More preferably, the temperature of the hydrothermal reaction in step S3 is 100 to 150 ℃ and the reaction time is 8 to 12 hours.
The invention also provides the NH2The application of the-MIL-101 (Fe) @ SNW-1 composite catalyst in hydrogen production by photocatalytic cracking water has the advantages of strong hydrogen production capacity, high stability and recycling.
The invention has the beneficial effects that: NH provided by the invention2-MIL-101(Fe) @ SNW-1 composite catalyst and NH2MIL-101(Fe) has a larger specific surface area and a significantly enhanced light absorption capacity than SNW-1; and due to NH2MIL-101(Fe) and SNW-1 are connected through generating a new chemical bond (amido bond), a migration channel is provided for a photon-generated carrier, a Z-type heterojunction is formed, the photon-generated electron-hole recombination rate is greatly reduced, and the performance of hydrogen production through photocatalytic water splitting is obviously improved. In addition, the composite catalyst prepared by the invention has high stability, mainly comprising NH2The MIL-101(Fe) and the SNW-1 are bridged through an amido bond instead of through van der Waals interaction, so that the secondary pollution of a water body is avoided, and the preparation method is simple, easy to operate and low in production cost, so that the method has great potential in the aspect of practical application.
Drawings
FIG. 1 is an SEM image of a composite catalyst prepared in example 1 of the present invention;
FIG. 2 is a diagram showing the distribution of elements of the composite catalyst prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a composite catalyst prepared in example 1 of the present invention;
FIG. 4 is a graph representing the light absorption properties of a composite catalyst prepared in example 1 of the present invention;
FIG. 5 is an XPS spectrum of a composite catalyst prepared in example 1 of the present invention;
FIG. 6 is a graph showing the performance of photocatalytic hydrogen production by water splitting of the composite catalyst prepared in example 1;
fig. 7 is a characteristic diagram of the recycling performance of the photocatalytic water splitting hydrogen production performance of the composite catalyst prepared in example 1 of the present invention.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described with reference to the accompanying drawings and examples, which are only used for illustrating the technical solutions of the present invention more clearly and are not intended to limit the scope of the present invention.
Example 1
NH2-MIL-101(Fe) @ SNW-1 composite catalyst preparation, the process is as follows:
(1) 224.6mg NH2-H2BDC (2-aminoterephthalic acid, 1.24mmol) and 675mg FeCl3·6H2O (2.5mmol) was added to a 100mL glass liner containing 15mL DMF (N, N-dimethylformamide) and sonicated until the solid was completely dissolved. Then putting the mixture into a hydrothermal kettle, raising the temperature to 110 ℃, preserving the heat for 12 hours, and then naturally cooling. Centrifuging at 8,000rpm for 10 min to obtain brown black powder, soaking in DMF for 2 hr, soaking in ethanol for 4 hr, and vacuum drying to obtain the first precursor NH2-MIL-101(Fe)。
(2) 400mg of the first precursor is weighed and placed in a 60mL wide-mouth bottle, 20mL of ethanol is added for ultrasonic dispersion, 400mg of terephthalaldehyde (2.98mmol), 40mL of a mixed solution of 1, 2-dichlorobenzene and ethanol (v: v ═ 4:1) are added, and 2mL of a 3mol/L acetic acid solution is added after ultrasonic treatment for 5 minutes. Sealing the wide-mouth bottle with a silica gel plug, performing low-temperature freezing, performing air extraction, then refilling with high-purity nitrogen, and circulating the mixture 6Next, the gas was not inflated after the last evacuation (evacuation to prevent polymerization of terephthalaldehyde itself). Then putting the mixture into a hydrothermal kettle, raising the temperature to 85 ℃, preserving the heat for 16 hours, naturally cooling, and centrifuging by using a centrifugal machine to obtain a brown product. Washing the product with hot ethanol for multiple times, drying at low temperature to obtain a second precursor, and recording as NH2-MIL-101(Fe)(CHO)。
(3) An amount of the second precursor, 150mg terephthalaldehyde, 172mg melamine and 40mL1, 2-dichlorobenzene/ethanol (4:1 ═ v: v) were added to a 60mL jar and after 5 minutes sonication, 3-M acetic acid (0.8mL) was added. Then the wide-mouth bottle is sealed by a silica gel plug, the wide-mouth bottle is circularly vacuumized and filled with nitrogen for 6 times after being frozen at low temperature, and finally the wide-mouth bottle is placed into an autoclave in a vacuum state, heated to 110 ℃ and kept warm for 12 hours. The catalyst is collected by centrifuging at 8,000rpm for 10 minutes, then is washed by absolute ethyl alcohol, and is dried in vacuum to obtain brown powder, namely the composite catalyst which is recorded as MS-1.
In this example, 1, 2-dichlorobenzene and ethanol were used as a mixed solvent to promote dissolution and further promote the reaction to proceed smoothly. And (3) taking acetic acid as a catalyst to promote dehydration condensation reaction of the amino on the surface of the first precursor and terephthalaldehyde in the step (2), and promote condensation reaction of aldehyde on the surface of the second precursor and the amino in melamine in the step (3).
And (4) changing the adding amount of the second precursor in the step (3) to prepare the composite catalyst with different SNW-1 loading amounts, wherein the composite catalyst is 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 NH in the composite material2The ratios of the mass of MIL-101(Fe) to the mass of SNW-1 are 1:0.4, 1:0.6, 1:0.8 and 1:1, and if the loading is expressed in percentage, 29%, 38%, 44% and 50%, respectively (the loading is calculated as SNW-1 mass/total mass of composite material x 100%).
Comparative example 1
Pure NH2Preparation of MIL-101(Fe) nanomaterial, the preparation method being identical to step (1) of example 1.
Comparative example 2
The preparation of 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 sonication for 5 minutes, 3-M acetic acid (0.8mL) was added. Then the wide-mouth bottle is sealed by a silica gel plug, the wide-mouth bottle is circularly vacuumized and filled with nitrogen for 6 times after being frozen at low temperature, and finally the wide-mouth bottle is placed into an autoclave in a vacuum state, heated to 110 ℃ and kept warm for 12 hours. This was collected by centrifugation at 8,000rpm for 10 minutes, then washed with anhydrous ethanol, and dried under vacuum to give SNW-1 as a white powder.
The materials prepared in example 1 and the 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 were as follows:
shape characterization
Composite catalysts prepared in example 1 and comparative examples 1 to 2, and NH2And carrying out morphology characterization on MIL-101(Fe) and SNW-1, wherein the results are shown in figures 1-2.
FIG. 1 is NH2SEM spectra for MIL-101(Fe), SNW-1 and MS-1-0.8, from which: NH synthesized by hydrothermal method2MIL-101(Fe) is relatively uniform in size (shown in panel a); SNW-1 is spherical particles but not uniform enough in size (shown in b), probably due to different degrees of polymerization; interestingly, it is apparent from the c and d plots that SNW-1 is present in NH2The surface of MIL-101(Fe) is a hollow spherical structure when the surface is assembled step by step.
FIG. 2 is a SEM elemental distribution plot of MS-1-0.8, from which it can be seen that the major elements O, Fe and N are uniformly distributed on the core-shell material, indicating that SNW-1 has been successfully assembled in steps with NH2-MIL-101(Fe) on the surface.
Crystal phase characterization
The crystal structure and phase composition of each product in the examples and comparative examples were analyzed by PXRD diffraction, and the results are shown in fig. 3: NH (NH)2The positions of the diffraction peaks of MIL-101(Fe) occur at approximately 5 °, 9 ° and 13 °, and a broader characteristic peak at 23.8 ° for SNW-1, which is probably due to its own microporous polymer, poor crystalline form, which also leads to NH2Part of characteristic peak of MIL-101(Fe) is in MS-1-0.8 composite catalystThe cause of the shift.
③ characterization of light absorption property
The light absorption properties of the products of 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 the irradiation of ultraviolet light, and NH (NH)2MIL-101(Fe) and MS-1-0.8 both have strong light absorption capacity at 480 nm.
Chemical valence detection of elements in sample
The chemical valence state of the main elements in each product is researched by X-ray photoelectron spectroscopy (XPS), and MS-1-0.8, pure SNW-1 and NH are studied2XPS spectra of C1s, N1 s and Fe 2p were compared between MIL-101(Fe) samples, and the results are shown in FIG. 5.
The full spectrum scanning map is shown in a picture, NH2MIL-101(Fe) has mainly four elements of C, N, O and Fe, while for SNW-1 there are only two elements of C and N, and as for the presence of a small amount of O elements, it is due to background interference. Most importantly, d is a fine spectrum of Fe 2p, NH2The MIL-101(Fe) sample has two distinct peaks at the binding energies of 711.7eV and 726.0eV, which are respectively assigned to Fe 2p3/2And Fe 2p1/2In addition, a satellite peak at 716.5eV binding energy also belongs to Fe (III); MS-1-0.8 vs. NH2Fe 2p of MIL-101(Fe)3/2And Fe 2p1/2The binding energy was reduced by 0.2eV and 0.8eV, respectively, which fully indicates the N atom and NH in SNW-12The Fe ion in MIL-101(Fe) is coordinated.
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 into a 500mL quartz reactor, 100mL of water containing 50% methanol was added, and 5mL of H was added2PtCl6(Pt concentration: 0.1mg/ml) as a precursor, Pt was deposited on the catalyst surface by in-situ photo-deposition. An additional 15mL of TEOA was added as a sacrificial agent. The catalyst was dispersed in the solution by magnetic stirring for 10 minutes before light irradiationAnd (4) uniformity. Blowing N into the sealed system for 20 minutes2To try to remove air from the system. Then irradiated using a 300W xenon lamp (Perfect Light, PLS-SXE300C, Beijing). The gas in the reaction system was taken every 30 minutes and detected by gas chromatography (GC9700, Techcomp).
As a control, NH in pure form was detected in the same manner as described above2The catalytic hydrogen production performance of MIL-101(Fe) and SNW-1.
Fig. 6 shows the photocatalytic hydrogen production and hydrogen production efficiency of the shell-core nanocomposite catalysts with different loading amounts under simulated sunlight. As can be seen from graph a, NH in the pure state2The photocatalytic hydrogen production activities of MIL-101(Fe) and SNW-1 are both low, and the hydrogen production in 4 hours is 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 as high as 6669.88, 7082.45, 7798.25 and 6609.31 mu molg-1The hydrogen production rates are 1667.47, 1770.61, 1949.56 and 1652.33 mu mol h respectively-1g-1Wherein the highest hydrogen production activity is MS-1-0.8.
(2) Stability detection of photocatalytic hydrogen production
The operation of the circulation experiment of photocatalytic hydrogen production is consistent with that of the step (1), except that MS-1-0.8 is only 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 experiments show that the MS-1-0.8 can maintain high photocatalytic hydrogen production activity in four cycles of hydrogen production, and the four hydrogen production amounts are 7898.85, 7704.67, 7556.51 and 7689.08 mu mol/g respectively. The cycle experiment results show that the prepared shell-core composite catalyst MS-1-0.8 has better stability in the photocatalysis process and has potential application value in the aspect of photocatalytic hydrogen production.
In summary, with NH2The increase in photocatalytic activity of the composite catalyst compared to MIL-101(Fe) and SNW-1 is attributed to NH2One of MIL-101(Fe) and SNW-1Are bridged by amide bonds, rather than simple physical mixing. In addition, experiments prove that the adjustment of the preparation process parameters within the small range given in the specification has no significant influence on the catalytic performance of the product.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. Preparation of NH2-MIL-101(Fe) @ SNW-1 composite catalyst, characterized in that it is: to NH2Aldehyde modification is carried out on the surface of-MIL-101 (Fe), and then the aldehyde modification, terephthalaldehyde and melamine are mixed to carry out hydrothermal reaction to obtain NH2-MIL-101(Fe) surface amide bond is connected with SNW-1 composite catalyst.
2. Preparation of NH according to claim 12-MIL-101(Fe) @ SNW-1 composite catalyst, characterized in that it comprises in particular the following steps:
s1, adding 2-amino terephthalic acid and FeCl by taking DMF as a solvent3·6H2O, performing hydrothermal reaction after uniformly mixing to obtain a first precursor;
s2, dispersing the first precursor in ethanol, adding terephthalaldehyde and 1, 2-dichlorobenzene, performing vacuum-pumping treatment, and performing hydrothermal reaction to obtain a second precursor;
s3, taking the mixed solution of 1, 2-dichlorobenzene and ethanol as a solvent, adding the second precursor, terephthalaldehyde and melamine into the solvent, uniformly mixing, vacuumizing, and carrying out hydrothermal reaction to obtain the composite catalyst.
3. Preparation of NH according to claim 22-MIL-101(Fe) @ SNW-1 composite catalyst, characterized in that the 2-aminoterephthalic acid and FeCl are mixed in step S13·6H2The molar ratio of O is 1: 1.8-2.2.
4. Preparation of NH according to claim 22The method of the-MIL-101 (Fe) @ SNW-1 composite catalyst is characterized in that the molar ratio of the first precursor to terephthalaldehyde in the step S2 is 1: 1.5-2.2.
5. Preparation of NH according to claim 22The method of the-MIL-101 (Fe) @ SNW-1 composite catalyst is characterized in that the molar ratio of the second precursor to the terephthalaldehyde to the melamine in the step S3 is 1: 1-4.
6. Preparation of NH according to claim 22The method of the-MIL-101 (Fe) @ SNW-1 composite catalyst is characterized in that the temperature of the hydrothermal reaction in the step S2 is 80-120 ℃, and the reaction time is 12-24 h.
7. Preparation of NH according to claim 22The method of the-MIL-101 (Fe) @ SNW-1 composite catalyst is characterized in that the temperature of the hydrothermal reaction in the step S3 is 100-150 ℃, and the reaction time is 8-12 h.
8. NH prepared according to any one of claims 1 to 72MIL-101(Fe) @ SNW-1 composite catalyst.
9. The NH of claim 82Application of-MIL-101 (Fe) @ SNW-1 composite catalyst in hydrogen production by photocatalytic water decomposition.
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