CN112079995B - Transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst - Google Patents
Transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst Download PDFInfo
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title abstract description 21
- -1 Transition metal modified pyridine nitrogen Chemical class 0.000 title abstract description 13
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 150000003624 transition metals Chemical group 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- VCHOFVSNWYPAEF-UHFFFAOYSA-N 1-(3-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(C(C)=O)=C1 VCHOFVSNWYPAEF-UHFFFAOYSA-N 0.000 claims description 13
- SUQGULAGAKSTIB-UHFFFAOYSA-N 6-(5-formylpyridin-2-yl)pyridine-3-carbaldehyde Chemical compound N1=CC(C=O)=CC=C1C1=CC=C(C=O)C=N1 SUQGULAGAKSTIB-UHFFFAOYSA-N 0.000 claims description 13
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 11
- 239000005695 Ammonium acetate Substances 0.000 claims description 11
- 229940043376 ammonium acetate Drugs 0.000 claims description 11
- 235000019257 ammonium acetate Nutrition 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 5
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000547 conjugated polymer Polymers 0.000 claims 3
- 230000001699 photocatalysis Effects 0.000 abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005576 amination reaction Methods 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 6
- 238000007740 vapor deposition Methods 0.000 abstract description 6
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical class [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical class NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 238000004868 gas analysis Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 108010015780 Viral Core Proteins Proteins 0.000 description 1
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- 239000012159 carrier gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- NQLVCAVEDIGMMW-UHFFFAOYSA-N cyclopenta-1,3-diene;cyclopentane;nickel Chemical compound [Ni].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 NQLVCAVEDIGMMW-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention relates to a transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst, which is prepared by aldehyde-ketone condensation, conjugate addition and cyclic amination reaction of a transition metal-iron, cobalt, nickel and pyridine nitrogen-based conjugated microporous polymer, and is prepared by a vapor deposition method, so that the transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst has good application in photolysis for water and hydrogen production. The photocatalyst obtained by the invention has good photocatalytic hydrogen production performance and high hydrogen production rate; the invention adopts a vapor deposition method, and has simple process, simple equipment and simple operation.
Description
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst.
Background
Energy and environment are two major core problems facing the world at present, and human life and technological development are closely related to energy. A large amount of greenhouse gases are emitted during combustion of traditional fossil energy, and the environment is seriously damaged, so that novel clean energy is urgently needed to be found. Hydrogen can help to solve global environmental pollution and energy safety problems, thus becoming an ideal substitute for traditional energy. Wherein, the photocatalytic water decomposition is the main path for hydrogen production, and the photocatalytic technology becomes an effective means for solving the energy and environmental problems in the future.
The conjugated microporous polymer is a rigid macromolecule formed by regularly linking aromatic rings through pi-pi bonds, and has a unique conjugated structure and micropores with the permanence of less than 2 nm. The pore property of the material is closely related to the structure of a rigid monomer, and simultaneously, the material shows better physical and chemical stability and thermal stability than the traditional microporous material due to irreversible reaction. Nevertheless, the general conjugated microporous polymers still do not have excellent photocatalytic hydrogen evolution performance.
The prior Chinese patent CN105367758A discloses a preparation method of ferrocenyl conjugated microporous polymer, which has complex preparation process, uses high-cost metal as a catalyst and has no universality. The invention overcomes the defects, and provides the transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst which is simple to operate, low in cost and has certain universality.
Disclosure of Invention
The invention aims to solve the technical problem of providing a transition metal modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst, and overcomes the defects of complex operation, high preparation cost, no universality and the like in the prior art.
The invention relates to a pyridine nitrogen-based conjugated microporous polymer, which comprises the following repeating structural units:
The structural formula of the polymer is as follows:
The pyridine nitrogen-based conjugated microporous polymer is obtained by performing aldehyde-ketone condensation, conjugate addition and cyclic amination on raw materials containing 2,2 '-bipyridine-5, 5' -dicarboxaldehyde and 1, 3-diacetylbenzene.
The invention discloses a preparation method of a pyridine nitrogen-based conjugated microporous polymer, which comprises the following steps:
adding 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, 1, 3-diacetylbenzene and ammonium acetate into a reactor, adding pyridine, stirring at normal temperature, performing oil bath reaction, and purifying to obtain the product.
The preferred mode of the above preparation method is as follows:
the proportion of the 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, the 1, 3-diacetylbenzene, the ammonium acetate and the pyridine is 0.2-3 g: 0.3-4 g: 2-12 g: 35-300 mL.
Furthermore, the adding amount of the 2,2 '-bipyridine-5, 5' -dicarboxaldehyde is 0.2-3 g, the adding amount of the 1, 3-diacetylbenzene is 0.3-4 g, the adding amount of the ammonium acetate is 2-12 g, and the mixture is added into a 50-500 mL round-bottom flask.
The normal-temperature stirring comprises the following steps: stirring for 10-40 min at normal temperature until the solid matter is completely dissolved.
The oil bath reaction is as follows: and (3) heating the oil bath kettle to 100-130 ℃, reacting for 20-50 h, and performing suction filtration and washing to obtain powder.
The purification specifically comprises the following steps: and sequentially washing the obtained powder in hot deionized water and chloroform, carrying out suction filtration, and drying in a vacuum oven, wherein the temperatures of the deionized water and the chloroform for washing are heated to 50-80 ℃, washing for 15-60 h, carrying out suction filtration, and drying in the vacuum oven for 20-96 h.
The invention relates to a pyridine nitrogen-based conjugated microporous polymer composite catalyst, which is a pyridine nitrogen-based conjugated microporous polymer with a surface modified with transition metal.
The transition metal is one or more of Fe, Co and Ni.
The invention discloses a preparation method of a pyridine nitrogen-based conjugated microporous polymer composite catalyst, which comprises the following steps:
and (3) putting the transition metal precursor and the pyridine nitrogen-based conjugated microporous polymer into a tubular furnace in front and at back, heating in a nitrogen atmosphere, and cooling to room temperature along with the furnace to obtain the composite catalyst.
The preferred mode of the above preparation method is as follows:
the transition metal precursor is one or more of nickelocene, cobaltocene and ferrocene.
The mass percentage of the transition metal precursor and the obtained pyridine nitrogen-based conjugated microporous polymer is 5-50 wt%. (the mass of the transition metal precursor/the mass of the pyridine nitrogen-based conjugated microporous polymer is 5 wt% to 50 wt%).
The heating is specifically as follows: in the atmosphere of high-purity nitrogen (99.999%), heating to 100-300 ℃ at the heating rate of 1-6 ℃/min, and preserving heat for 1-4 h.
The pyridine nitrogen-based conjugated microporous polymer composite catalyst is applied to hydrogen production through photolysis.
Advantageous effects
(1) Uniformly modifying transition metal on the pyridine nitrogen-based conjugated microporous polymer for the first time;
(2) the photocatalyst prepared by the invention has good photocatalytic hydrogen production performance and high hydrogen production rate;
(3) the invention adopts the vapor deposition method to prepare the photocatalyst, and has simple process, simple equipment and simple operation;
(4) the novel photocatalyst developed by the invention introduces pyridine nitrogen into the conjugated microporous polymer, anchors transition metal, and has good performance of photocatalytic water decomposition to produce hydrogen under the irradiation of ultraviolet light and visible light. The pyridine nitrogen-based conjugated microporous polymer is synthesized by aldehyde-ketone condensation, conjugate addition and cyclic amination, and then the composite photocatalyst of the transition metal modified pyridine nitrogen-based conjugated microporous polymer is prepared by adopting a vapor deposition method. The photocatalyst has good performance of decomposing water to produce hydrogen.
(5) The transition metal and pyridine nitrogen-based conjugated microporous polymer is subjected to vapor deposition in a nitrogen atmosphere, so that the transition metal is uniformly modified on the surface of the pyridine nitrogen-based conjugated microporous polymer, and the highest average hydrogen production rate of the prepared transition metal modified pyridine nitrogen-based conjugated microporous polymer photocatalyst is 4.4mmol/(g.h), which is 1.73 times higher than that of the pure pyridine nitrogen-based conjugated microporous polymer. Compared with the prior art, the invention uniformly modifies the transition metal on the pyridine nitrogen-based conjugated microporous polymer for the first time; the obtained photocatalyst has good photocatalytic hydrogen production performance and high hydrogen production rate; the invention adopts a vapor deposition method, and has simple process, simple equipment and simple operation.
Drawings
FIG. 1 is a diagram of a process for forming a transition metal-modified pyridyl nitrogen-based conjugated microporous polymer; wherein the symbol in the m-PCMP structural formula represents an omitted repeating unit;
FIG. 2 shows a pyridine nitrogen-based conjugated microporous polymer13C-NMR chart;
FIG. 3 is a TEM and mapping image of a nickel-modified pyridazone-based conjugated microporous polymer (example 1): wherein (a) is a TEM image of the nickel-modified pyridazone-based conjugated microporous polymer, (b) is a distribution diagram of an element C in the image (a), (C) is a distribution diagram of an element C in the image (a), (d) is a distribution diagram of an element O in the image (a), and (e) is a distribution diagram of an element Ni in the image (a);
in FIG. 4, curves 1 and 2 are N of the pyridylamine-based conjugated microporous polymer and the nickel-modified pyridylamine-based conjugated microporous polymer (example 1) at 77.4K2Adsorption-desorption curve of (a);
in FIG. 5, the curves 1, 2, 3 and 4 are the infrared spectra of 2,2 '-bipyridine-5, 5' -dicarbaldehyde, 1, 3-diacetylbenzene, the prepared pyridinyloxy conjugated microporous polymer and the nickel-modified pyridinyloxy conjugated microporous polymer (example 1), respectively;
in fig. 6, curve 1, curve 2 and curve 3 are respectively hydrogen production rate curves of nickelocene, the prepared pyridyl conjugated microporous polymer and the nickel-modified pyridyl nitrogen-based conjugated microporous polymer (example 1);
in fig. 7, curves 1, 2, 3, and 4 are hydrogen production rate curves of the prepared pyridylazine-based conjugated microporous polymer, nickel-modified pyridylazine-based conjugated microporous polymer (example 1), iron-modified pyridylazine-based conjugated microporous polymer (example 2), and cobalt-modified pyridylazine-based conjugated microporous polymer (example 3), respectively.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
2,2 '-bipyridine-5, 5' -dicarbaldehyde was purchased from kaiyi, pyridine and ammonium acetate were purchased from the national pharmacy group, triethanolamine, 1, 3-diacetylbenzene, dicyclopentadienyl nickel, ferrocene were purchased from mikan, cobaltocene was purchased from Strem, chloroplatinic acid was purchased from sigma; the polymer pore size test was determined by micromeritics ASAP 2460; the photocatalytic hydrogen production experiment adopts a Labsolar 6A full-glass automatic micro-online gas analysis system, a 300W xenon lamp (Perfect Light PLS-SXE 300) is used as a Light source, and a gas chromatograph adopts a 9790II instrument (thermal conductivity detector TCD, Ar carrier gas) to measure precipitated H2Amount of the compound (A).
Example 1
(1) 0.636g of 2,2 '-bipyridine-5, 5' -dicarbaldehyde, 0.973g of 1, 3-diacetylbenzene and 6.9g of ammonium acetate were added to a 250mL round bottom flask;
(2) adding 150mL of pyridine into the round-bottom flask in the step (1), and stirring for 20min at normal temperature until the solid matter is completely dissolved;
(3) after the solid matter is dissolved, putting the round-bottom flask obtained in the step (2) into an oil bath kettle at the temperature of 115 ℃ for reaction for 24 hours, and performing suction filtration and washing to obtain powder;
(4) washing the obtained powder in deionized water and chloroform at 60 ℃ for 24 hours in sequence, performing suction filtration, and drying in a vacuum oven for 72 hours to obtain the pyridine nitrogen-based conjugated microporous polymer;
the pyridine nitrogen-based conjugated microporous polymer prepared in the step (4) has a structural formula as follows:
(5) putting the nickel cyclopentadienyl and the obtained pyridine nitrogen-based conjugated microporous polymer into a tubular furnace in a flat manner according to the mass percent of 30 wt%, heating to 150 ℃ at the heating rate of 2 ℃/minn in the atmosphere of high-purity nitrogen (99.999%), preserving heat for 2 hours, and finally cooling to room temperature along with the furnace to obtain the final nickel-modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst.
The performance test of hydrogen production by photocatalytic water decomposition is carried out as follows: using 3 wt% Pt as a co-catalyst and Triethanolamine (TEOA) as a sacrificial agent, 10mg of nickel-modified pyridylazine-based conjugated microporous polymer was dispersed in 50mL of a solution containing 3 wt% Pt and 10% vol TEOA, transferred to a photocatalytic reactor after 30min of sonication, and evacuated for 1h to remove oxygen from the solution. The precipitated H was measured by gas chromatography under irradiation of a 300W xenon lamp2Amount of the compound (A). And (3) calculating to obtain a relation curve graph of the hydrogen production rate along with the photocatalytic time (as shown in a curve 3 in figure 6).
Method for preparing pyridine nitrogen-based conjugated microporous polymer obtained in example13As shown in fig. 2, the C-NMR measurement results showed that the carbonyl groups of some monomers were not completely reacted due to hindrance by steric hindrance or the like, and a weak carbonyl group (-C ═ O-) peak was observed at-164 ppm; resonance peaks of 154ppm and 147ppm are respectively derived from carbon at ortho-position and para-position of nitrogen in the pyridine ring; peaks at 135, 126, 120ppm correspond to the pyridine nitrogen meta-position, the benzene ring, the carbon connecting the two pyridine rings, respectively.
The infrared spectra of the pyridylamine-based conjugated microporous polymer and the nickel-modified pyridylamine-based conjugated microporous polymer obtained in this example are shown in fig. 5 as curve 3 and curve 4, and the chemical structures of the polymers themselves are not changed after nickel modification. At-1600 cm-1The absorption peak at which-C ═ N-bonds were formed confirms the formation of pyridine rings, indicating the smooth progress of the cyclic amination reaction. At-1680 cm-1the-C ═ O-absorption peak at (A) is derived from the residue of the monomer, but it can be observed that it is markedly attenuated compared with the monomer, and therefore binding is observed13C-NMR gave the structure of the above-mentioned pyridylazine-based polymer.
The pyridine nitrogen-based conjugated microporous polymer and the nickel-modified pyridine nitrogen-based conjugated microporous polymer obtained in the embodiment have N under 77.4K2The adsorption and desorption curves of (1) and (2) are shown in FIG. 4, and the curves represent typical type I/IV and are in a low pressure range (p/p)0<0.5)N2The adsorption amount sharply rises, demonstrating the presence of a microporous structure in the polymer. A section of rapidly enhanced adsorption value exists in a high-pressure range, and is mainly originated from macropores and mesopores formed by stacking among particles in the polymer, so that a pore channel which is more favorable for charge transmission is provided. The specific surface area of the pyridine nitrogen-based conjugated microporous polymer is 323.98m2Per g, pore volume 0.3cm3(ii)/g; after nickel modification, the pore channels of the conjugated microporous polymer are used for anchoring nickel, so that the specific surface area is reduced to 100.27m2Per g, pore volume 0.13cm3/g。
The TEM and mapping patterns of the nickel-modified pyridine nitrogen-based conjugated microporous polymer obtained in this example are shown in fig. 3, and nickel element cannot be found in fig. 3(a), possibly because of the small size of nickel. And through mapping graphs (b) to (e) in fig. 3, it can be seen that carbon, nitrogen, oxygen and nickel elements are uniformly distributed on the pyridinylamino conjugated microporous polymer, which proves that the nickel elements are successfully modified in the pyridinylamino conjugated microporous polymer.
The nickelocene in this embodiment has no photocatalytic hydrogen generation performance (as shown in curve 1 in fig. 6), the hydrogen production rate of the pyridylazine-based conjugated microporous polymer is 2.54mmol/(g.h) (as shown in curve 2 in fig. 6), and the average hydrogen production rate of the nickel-modified pyridylazine-based conjugated microporous polymer is 4.42mmol/(g.h) (as shown in curve 3 in fig. 6), so that the hydrogen production rate of the nickel-modified pyridylazine-based conjugated microporous polymer is increased by 1.73 times.
Example 2
(1) 0.636g of 2,2 '-bipyridine-5, 5' -dicarbaldehyde, 0.973g of 1, 3-diacetylbenzene and 6.9g of ammonium acetate were added to a 250mL round bottom flask;
(2) adding 150mL of pyridine into the round-bottom flask in the step (1), and stirring for 20min at normal temperature until the solid matter is completely dissolved;
(3) after the solid matter is dissolved, putting the round-bottom flask obtained in the step (2) into an oil bath kettle at the temperature of 115 ℃ for reaction for 24 hours, and performing suction filtration and washing to obtain powder;
(4) washing the obtained powder in deionized water and chloroform at 60 ℃ for 24 hours in sequence, performing suction filtration, and drying in a vacuum oven for 72 hours to obtain the pyridine nitrogen-based conjugated microporous polymer;
(5) and horizontally discharging ferrocene and the obtained pyridine nitrogen-based conjugated microporous polymer into a tubular furnace according to the mass percent of 30 wt%, heating to 150 ℃ at the heating rate of 2 ℃/minn in the atmosphere of high-purity nitrogen (99.999%), preserving heat for 2 hours, and finally cooling to room temperature along with the furnace to obtain the final iron-modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst.
The performance test of photocatalytic water decomposition hydrogen production is carried out at room temperature: using 3 wt% Pt as a co-catalyst and Triethanolamine (TEOA) as a sacrificial agent, 10mg of the iron-modified pyridylazine-based conjugated microporous polymer was dispersed in 50mL of a solution containing only 10% vol TEOA, sonicated for 30min and then transferred to a photocatalytic reactor, and evacuated for 1h to remove oxygen from the solution. The precipitated H was measured by gas chromatography under irradiation of a 300W xenon lamp2Amount of the compound (A). And (3) calculating to obtain a relation curve graph of the hydrogen production rate along with the photocatalytic time (as shown in a curve 3 in figure 7). The result shows that the photocatalytic average hydrogen production rate of the iron-modified pyridine nitrogen-based conjugated microporous polymer obtained in the embodiment is 3.42mmol/(g.h), and is improved by 1.35 times compared with 2.54mmol/(g.h)) of the pyridine nitrogen-based conjugated microporous polymer before modification (as shown in fig. 7, curve 1).
Example 3
(1) 0.636g of 2,2 '-bipyridine-5, 5' -dicarbaldehyde, 0.973g of 1, 3-diacetylbenzene and 6.9g of ammonium acetate were added to a 250mL round bottom flask;
(2) adding 150mL of pyridine into the round-bottom flask in the step (1), and stirring for 20min at normal temperature until the solid matter is completely dissolved;
(3) after the solid matter is dissolved, putting the round-bottom flask obtained in the step (2) into an oil bath kettle at the temperature of 115 ℃ for reaction for 24 hours, and performing suction filtration and washing to obtain powder;
(4) washing the obtained powder in deionized water and chloroform at 60 ℃ for 24 hours in sequence, performing suction filtration, and drying in a vacuum oven for 72 hours to obtain the pyridine nitrogen-based conjugated microporous polymer;
(5) placing cobaltocene and the obtained pyridine nitrogen-based conjugated microporous polymer into a tubular furnace according to the mass percent of 30 wt%, heating to 150 ℃ at the heating rate of 2 ℃/minn in the atmosphere of high-purity nitrogen (99.999%), preserving heat for 2 hours, and finally cooling to room temperature along with the furnace to obtain the final cobalt-modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst.
The performance test of photocatalytic water decomposition hydrogen production is carried out at room temperature: using 3 wt% Pt as a co-catalyst and Triethanolamine (TEOA) as a sacrificial agent, 10mg of cobalt-modified pyridazone-based conjugated microporous polymer was dispersed in 50mL of a solution containing 3 wt% Pt and 10% vol TEOA, transferred to a photocatalytic reactor after 30min of sonication, and evacuated for 1h to remove oxygen from the solution. The precipitated H was measured by gas chromatography under irradiation of a 300W xenon lamp2Amount of the compound (A). And calculating to obtain a relation curve of the hydrogen production rate with the photocatalysis time (as shown in a curve 4 in figure 7). The result shows that the photocatalytic average hydrogen production rate of the cobalt-modified pyridine nitrogen-based conjugated microporous polymer obtained in the embodiment is 2.82mmol/(g.h), and is improved by 1.11 times compared with 2.54mmol/(g.h)) of the pyridine nitrogen-based conjugated microporous polymer before modification (as shown in fig. 7, curve 1).
Example 4
(1) 0.318g of 2,2 '-bipyridine-5, 5' -dicarbaldehyde, 0.4865g of 1, 3-diacetylbenzene and 3.5g of ammonium acetate were added to a 250mL round bottom flask;
(2) adding 120mL of pyridine into the round-bottom flask in the step (1), and stirring for 15min at normal temperature until the solid matter is completely dissolved;
(3) after the solid matter is dissolved, putting the round-bottom flask in the step (2) into an oil bath kettle at the temperature of 120 ℃ for reaction for 20 hours, and filtering and washing to obtain powder;
(4) washing the obtained powder in deionized water and chloroform at 70 ℃ for 18h in sequence, filtering, and drying in a vacuum oven for 48h to obtain the pyridine nitrogen-based conjugated microporous polymer;
(5) putting the nickel cyclopentadienyl and the obtained pyridine nitrogen-based conjugated microporous polymer into a tubular furnace in a mass percent of 50 wt%, heating the tubular furnace to 120 ℃ at a heating rate of 3 ℃/minn in a high-purity nitrogen (99.999%) atmosphere, preserving the heat for 2 hours, and finally cooling the tubular furnace to room temperature to obtain the final nickel-modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst.
The performance test of photocatalytic water decomposition hydrogen production is carried out at room temperature: using chloroplatinic acid hexahydrate (H)2PtCl6.6H2O) as a cocatalyst, Triethanolamine (TEOA) as a sacrificial agent, 10mg of nickel-modified pyridylazine-based conjugated microporous polymer was dispersed in 50mL of a solution containing 3 wt% Pt and 10% vol TEOA, sonicated for 30min and then transferred to a photocatalytic reactor. And connecting a Labsolar 6A full-glass automatic trace on-line gas analysis system, and vacuumizing for 1h to remove oxygen in the solution. The precipitated H was measured by a gas chromatograph under irradiation of a 300W xenon lamp2Amount of the compound (A). And calculating to obtain a relation curve of the hydrogen production rate along with the photocatalytic time (as shown in a curve 2 in figure 8). The result shows that the photocatalytic average hydrogen production rate of the nickel-modified pyridine nitrogen-based conjugated microporous polymer obtained in the embodiment is 3.24mmol/(g.h), and is improved by 1.28 times compared with 2.54mmol/(g.h)) of the pyridine nitrogen-based conjugated microporous polymer before modification (as shown in fig. 8, curve 1).
Example 5
(1) 1.06g of 2,2 '-bipyridine-5, 5' -dicarbaldehyde, 1.62g of 1, 3-diacetylbenzene and 11.5g of ammonium acetate were added to a 500mL round bottom flask;
(2) adding 250mL of pyridine into the round-bottom flask in the step (1), and stirring at normal temperature for 40min until the solid matter is completely dissolved;
(3) after the solid matter is dissolved, putting the round-bottom flask obtained in the step (2) into an oil bath kettle at 125 ℃ for reaction for 48 hours, and performing suction filtration and washing to obtain powder;
(4) washing the obtained powder in deionized water and chloroform at 70 ℃ for 50h in sequence, carrying out suction filtration, and drying in a vacuum oven for 90h to obtain the pyridine nitrogen-based conjugated microporous polymer;
(5) putting the nickel cyclopentadienyl and the obtained pyridine nitrogen-based conjugated microporous polymer into a tubular furnace in a horizontal arrangement mode according to the mass percent of 20 wt%, heating to 300 ℃ at the heating rate of 6 ℃/minn in the atmosphere of high-purity nitrogen (99.999%), preserving heat for 4 hours, and finally cooling to the room temperature along with the furnace to obtain the final nickel-modified pyridine nitrogen-based conjugated microporous polymer composite photocatalyst.
The performance test of photocatalytic water decomposition hydrogen production is carried out at room temperature: using 3 wt% Pt as a co-catalyst and Triethanolamine (TEOA) as a sacrificial agent, 10mg of nickel-modified pyridylazine-based conjugated microporous polymer was dispersed in 50mL of a solution containing 3 wt% Pt and 10% vol TEOA, transferred to a photocatalytic reactor after 30min of sonication, and evacuated for 1h to remove oxygen from the solution. The precipitated H was measured by gas chromatography under irradiation of a 300W xenon lamp2Amount of the compound (A). The hydrogen production was calculated as a function of the photocatalytic time (as shown in fig. 8, curve 3). The result shows that the photocatalytic average hydrogen production rate of the nickel-modified pyridine nitrogen-based conjugated microporous polymer obtained in the embodiment is 4.05mmol/(g.h), and is improved by 1.59 times compared with 2.54mmol/(g.h)) of the pyridine nitrogen-based conjugated microporous polymer before modification (as shown in fig. 8, curve 1).
Claims (7)
1. The pyridine nitrogen-based conjugated microporous polymer composite catalyst is characterized in that the composite catalyst is a pyridine nitrogen-based conjugated microporous polymer with a surface modified with transition metal;
wherein, the pyridine nitrogen-based conjugated microporous polymer composite catalyst is prepared by the following method:
putting a transition metal precursor and a pyridine nitrogen-based conjugated microporous polymer into a tubular furnace from front to back, heating in a nitrogen atmosphere, and cooling to room temperature along with the furnace to obtain a composite catalyst; the transition metal precursor is one or more of nickelocene, cobaltocene and ferrocene; the transition metal precursor accounts for 5-50 wt% of the pyridine nitrogen-based conjugated microporous polymer; the heating is specifically as follows: in a high-purity nitrogen atmosphere, heating to 100-300 ℃ at a heating rate of 1-6 ℃/min, and keeping the temperature for 1-4 h;
wherein the repeating structural unit of the pyridine nitrogen-based conjugated polymer is as follows:
2. the composite catalyst as claimed in claim 1, wherein the pyridine nitrogen-based conjugated polymer has a structural formula:
3. the composite catalyst according to claim 1, wherein the pyridylazine-based conjugated microporous polymer is prepared by a process comprising:
adding 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, 1, 3-diacetylbenzene and ammonium acetate into a reactor, adding pyridine, stirring at normal temperature, performing oil bath reaction, and purifying to obtain the product.
4. The composite catalyst according to claim 3, wherein the ratio of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, 1, 3-diacetylbenzene, ammonium acetate and pyridine is 0.2-3 g: 0.3-4 g: 2-12 g: 35-300 mL.
5. The composite catalyst according to claim 1, wherein the transition metal is one or more of Fe, Co and Ni.
6. A method for preparing the pyridine nitrogen-based conjugated microporous polymer composite catalyst according to claim 1, comprising:
putting a transition metal precursor and a pyridine nitrogen-based conjugated microporous polymer into a tubular furnace from front to back, heating in a nitrogen atmosphere, and cooling to room temperature along with the furnace to obtain a composite catalyst; wherein the transition metal precursor is one or more of nickelocene, cobaltocene and ferrocene; the transition metal precursor accounts for 5-50 wt% of the pyridine nitrogen-based conjugated microporous polymer; the heating is specifically as follows: in a high-purity nitrogen atmosphere, heating to 100-300 ℃ at a heating rate of 1-6 ℃/min, and keeping the temperature for 1-4 h;
wherein the repeating structural unit of the pyridine nitrogen-based conjugated polymer is as follows:
7. the use of the pyridine nitrogen-based conjugated microporous polymer composite catalyst according to claim 1 in hydrogen production through photolysis.
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