CN117106162A - Triazole triazinyl-based conjugated microporous polymer and application thereof - Google Patents
Triazole triazinyl-based conjugated microporous polymer and application thereof Download PDFInfo
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- CN117106162A CN117106162A CN202311368364.0A CN202311368364A CN117106162A CN 117106162 A CN117106162 A CN 117106162A CN 202311368364 A CN202311368364 A CN 202311368364A CN 117106162 A CN117106162 A CN 117106162A
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 65
- 230000001699 photocatalysis Effects 0.000 claims abstract description 36
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003852 triazoles Chemical class 0.000 claims abstract description 25
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 23
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- AAORDHMTTHGXCV-UHFFFAOYSA-N uranium(6+) Chemical compound [U+6] AAORDHMTTHGXCV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 10
- -1 boric acid ester compound Chemical class 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 claims abstract description 4
- 229910052770 Uranium Inorganic materials 0.000 claims description 37
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000000605 extraction Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- YMZMDMWMKVPGDP-UHFFFAOYSA-N 5-(4-bromophenyl)-2h-tetrazole Chemical compound C1=CC(Br)=CC=C1C1=NNN=N1 YMZMDMWMKVPGDP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- HNVACBPOIKOMQP-UHFFFAOYSA-N uranium(4+) Chemical compound [U+4] HNVACBPOIKOMQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 230000005281 excited state Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000005286 illumination Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000013307 optical fiber Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000013535 sea water Substances 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 125000005605 benzo group Chemical group 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000002452 interceptive effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 238000007540 photo-reduction reaction Methods 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LIZOFKWBNVAHPD-UHFFFAOYSA-N 2h-triazolo[4,5-d]triazine Chemical compound C1=NN=NC2=C1NN=N2 LIZOFKWBNVAHPD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 208000017983 photosensitivity disease Diseases 0.000 description 2
- 231100000434 photosensitization Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- WZYVDGDZBNQVCF-UHFFFAOYSA-N 2,4,6-tris(4-bromophenyl)-1,3,5-triazine Chemical compound C1=CC(Br)=CC=C1C1=NC(C=2C=CC(Br)=CC=2)=NC(C=2C=CC(Br)=CC=2)=N1 WZYVDGDZBNQVCF-UHFFFAOYSA-N 0.000 description 1
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- BQYULTPOOHMNRM-UHFFFAOYSA-N anthracene-9,10-dione;perylene Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 BQYULTPOOHMNRM-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
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Abstract
The invention provides a triazole triazinyl-based conjugated microporous polymer and application thereof, and belongs to the technical field of photocatalytic function preparation. The preparation method is that triazole triazine triphenyl bromide and boric acid ester compound are combined in Pd (PPh) 3 ) 4 And polymerizing under catalysis, filtering, washing and Soxhlet extraction and purification of a reaction product to obtain the triazole triazinyl conjugated microporous polymer material. The triazole triazine conjugated microporous polymer has high specific surface area and excellent heat stability. The method further improves intersystem crossing rate and prolongs the service life of an excited state of the self-excited-state-type optical fiber, and has excellent photocatalysis performance when improving the charge transfer value of the spin orbit. Under the illumination condition, the uranium (VI) can be efficiently reduced and solidified, the conversion rate is up to 99 percent, the photocatalyst is easy to separate and recycle, and the recycling can be realizedHas important scientific research significance and practical application prospect.
Description
Technical Field
The invention belongs to the field of photocatalyst preparation, and particularly relates to a triazole triazinyl-based conjugated microporous polymer and application thereof.
Background
The porous organic polymer (Porous Organic Polymers, POPs) has high specific surface area, excellent thermal stability and chemical stability, good ultraviolet absorption performance and good photocatalytic activity, wherein the conjugated microporous polymer (Conjugated Microporous Polymers, CMPs) is an emerging functional material which is surrounded by a fully conjugated polymer network and has a microporous structure, has the common advantages of the porous organic polymer, and has a continuous conjugated pi-network structure, thereby being beneficial to photon absorption, exciton separation and charge transmission. CMPs have been favored in the field of photocatalysis due to their excellent photoelectric properties. Traditional methods for improving the photocatalytic activity of CMPs have focused more on studying charge transport and energy band regulation, and have less exploration of the key factor, intersystem crossing (InterSystem Crossing, ISC) that has a decisive influence on photocatalytic activity, and only a small part on reducing the singlet-Triplet energy level difference (Energy gap of the Singlet-Triplet states, Δe) ST ) To increase the ISC rate. Spin-Orbit Charge-transfer (SOC), which actually affects ISC dynamics, is rarely explored.
Currently, sea water is a huge liquid uranium ore, and scientists estimate that the sea water contains 45 hundred million tons of uranium, which is thousands of times of the ascertained uranium ore reserves on land, and the uranium is used as the most resource in nuclear energy, but the reserves in China are not abundant, and the quality of the uranium ore is mainly of medium and low grade, so that the scientists are also led to extensive researches. At present, CMPs are reported to be widely applied to reduction of uranium by a photocatalyst in literature, for example: the redox active perylene-anthraquinone conjugated microporous polymer has unique electron delocalization channel, and shows good photocatalytic activity in photocatalytic reduction of uranium (VI). However, the common factors such as high preparation cost, complex preparation process, low photocatalytic activity and the like of the conjugated microporous polymer prevent the conjugated microporous polymer from reducing metal uranium from further developing.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for constructing Conjugated Microporous Polymers (CMPs) by using a nitrogen enrichment strategy to improve the photocatalytic activity, and the triazole triazinyl conjugated microporous polymers are based on the triazole triazinyl conjugated microporous polymers, so that the charge separation efficiency is high, the increasing SOC value of the triazole triazinyl conjugated microporous polymers promotes the improvement of the ISC rate of the polymers, the excited state service life of the polymers is prolonged, and meanwhile, the reduction performance of uranium is also effectively improved.
In order to achieve the aim, the invention provides a triazole triazinyl-based conjugated microporous polymer, which is characterized in that the structural general formula of the polymer is shown as formula 1:
；
wherein R is selected from any one of structures shown in formulas 2-4:
。
preferably, the conjugated microporous polymer is in the form of powder or granule.
Preferably, the conjugated microporous polymers have SOC values of 0.41 and cm, respectively -1 ，0.1 cm -1 And 0.03 cm -1 。
Preferably, the excited state lives of the conjugated microporous polymer are respectively 30.5 mu s, 24.7 mu s and 18.3 mu s.
Preferably, the preparation method of the conjugated microporous polymer comprises the following steps:
s1, preparing triazole triazine triphenyl bromide: 5- (4-bromophenyl) -2HTetrazole, anhydrous K 2 CO 3 And cyanuric chloride are dissolved in 2-butanone, heated and stirred in an air atmosphere; after cooling to room temperature, the mixture was poured into water and extracted with dichloromethane; collecting an organic layer, washing, drying and purifying by using dichloromethane column chromatography to obtain triazole triazine triphenyl bromide;
s2, preparing a triazolyl triazinyl conjugated microporous polymer: triazole triazine triphenyl bromide prepared in the step S1, borate compound and K 2 CO 3 、Pd(PPh 3 ) 4 AndN,N-dimethylformamide is mixed, heated under the protection of inert gas, and cooled to room temperature after the reaction is finished to obtain a reaction mixture;
and S3, filtering, washing and further purifying the reaction mixture prepared in the step S2 by a Soxhlet extraction method, and vacuum drying to obtain the triazole triazinyl conjugated microporous polymer material.
Preferably, in the step S1, 5- (4-bromobenzene) -2HTetrazole, anhydrous K 2 CO 3 And the mass ratio of the cyanuric chloride is 3-4:8-9:1-1.8.
Preferably, the heating temperature in the step S1 is 90 ℃, and the stirring time is 48 hours; the extraction in the step S1 is repeated three times.
Preferably, in the step S2, the molar ratio of the triazole triazine triphenyl bromide to the borate compound is 2-3.1: 3-4.
Preferably, the heating reaction in the step S2 is to raise the temperature to 100-120 ℃ for 5 hours, and then raise the temperature to 135-155 ℃ for 24-48 hours.
Preferably, the soxhlet extraction time in the step S3 is 24 h and the vacuum drying temperature is 80 ℃.
Based on a general inventive concept, the present invention also provides an application method of the conjugated microporous polymer, comprising the following steps:
s1, dispersing a conjugated microporous polymer in uranium (VI) solution, and regulating the pH value to be 6;
and S2, continuously stirring the mixed solution obtained in the step S1 in the dark under the normal-temperature air atmosphere, and then reducing the photocatalytic uranium (VI) into uranium (IV) by using a xenon lamp as a light source.
Preferably, in the step S1, the concentration of the uranium (VI) solution is 50 to 100 ppm, and the uranium (VI) solution contains 10% by mass of methanol.
Preferably, the duration of stirring in the step S2 is 1 h, and the power of the xenon lamp is 300W.
The photocatalysis principle based on triazole triazinyl conjugated microporous polymer is as follows:
with triazole triazine triphenyl bromide (TTT) as a core, and respectively with benzo [ c ]][1，2，5]Polymerizing thiadiazole (BT), 2, 5-bithiophene (Th) and 1, 4-phenylene diboronic acid pinacol diester (Ph) to construct TTT-based polymer skeleton TTT-BT,TTT-Th and TTT-Ph. Under light excitation, the photosensitizer goes from the ground state (S 0 ) Excited to a singlet excited state (S 1 ) Then reaches a long-life triplet excited state (T 1 ). At T 1 In the state, the photosensitizer and molecular oxygen (O 2 ) Reactive Oxygen Species (ROS) are generated by the reaction, and T of the photosensitizer is prolonged by increasing ISC rate 1 Lifetime and thus help to generate O 2 •− 。
The SOC value of the enhanced CMPs is an effective strategy based on the design of an efficient photosensitizer of electron-mediated reaction, and the CMPs (TTT-BT, TTT-Ph, TTT-Th) functionalized by BT, ph and Th in the invention show higher photosensitization efficiency by utilizing the unique optical property of the donor-acceptor CMPs, and improve the ISC rate and prolong the excited state service life. Triazolyltriazinyl is largely achieved by enhancing the SOC capability of the polymer rather than reducing ΔE ST To regulate ISC rate, thus effectively improving the photocatalytic efficiency of CMPs.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a preparation method of a triazole triazine conjugated microporous polymer, which constructs TTT-based polymer frameworks TTT-BT, TTT-Th and TTT-Ph through a nitrogen enrichment strategy, expands an SOC value through the strategy of enriching the TTT framework through nitrogen to enhance ISC dynamics, so that the ISC dynamics generate photo-generated carriers with longer service life, and the photo-reduction process is driven better, so that the preparation substrate is wide.
(2) The triazole triazine conjugated microporous polymer provided by the invention utilizes the unique optical property generated by the interaction of a donor and a receptor thereof, improves the SOC value (0.41 cm) -1 ) Thus effectively promoting the ISC process and maintaining a longer excited state lifetime (up to 30.5 mus), thus exhibiting higher photosensitization efficiency, giving it excellent ability to photocatalytically reduce uranium (VI).
(3) The invention provides a conjugated microporous polymer based on triazolyl triazinyl, which has excellent ultraviolet absorption performance and good photocatalytic activity. Under the illumination condition, the method can efficiently catalyze uranium (VI) to be reduced, the conversion rate is up to 99 percent, and the conversion rate is obviously higher than that of conjugated microporous polymers based on benzo [ c ] [1,2,5] thiadiazole (BT).
(4) The conjugated microporous polymer prepared by the invention is easy to separate and recycle, can be recycled, widens the application of CMPs in the field of photocatalysis based on triazole triazine conjugated microporous polymer, and has important scientific research significance and practical application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments will be briefly described below. The drawings described below are merely examples of the present invention and other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is an infrared spectrum of triazole triazine triphenyl bromide (TTT-Br), benzo [ c ] [1,2,5] thiadiazole (BT) and triazole triazinyl conjugated microporous polymer based on TTT-BT in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of TTT-BT in example 1;
FIG. 3 is an electron paramagnetic resonance diagram of TTT-BT at 0 min, 5 min and 8 min in example 1;
fig. 4 is a graph of kinetic decay after pulse excitation at 485 nm in transient absorption at Ar (λem=450 nm) for TTT-BT in example 1;
FIG. 5 is a degradation curve of the photocatalytic seawater uranium extraction of Ph-BT, tr-BT and TTT-BT in experimental example 1;
FIG. 6 is a graph showing the dynamics of photocatalytic seawater uranium extraction from Ph-BT, tr-BT and TTT-BT in Experimental example 1;
FIG. 7 is a degradation graph of TTT-BT in experimental example 1 for photocatalytic seawater uranium extraction;
FIG. 8 is a graph showing degradation curves of different pH values in the photocatalytic seawater uranium extraction of TTT-BT in Experimental example 1;
FIG. 9 is a graph showing the recoverable performance of TTT-BT in experimental example 1 for the photocatalytic seawater uranium extraction;
FIG. 10 is a graph showing the photoreduction performance of U (VI) in the photocatalytic seawater uranium extraction of TTT-BT in Experimental example 1 in the presence of other interfering ions.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated; the reagents used in the examples were all commercially available unless otherwise specified.
Example 1 a triazolyltriazinyl-based conjugated microporous polymer TTT-BT was prepared.
S1, preparing triazole triazine triphenyl bromide (TTT-Br)
5- (4-bromophenyl) -2HTetrazole (3.3 g, 14.8 mmol), anhydrous K 2 CO 3 (8.2 g, 59.2 mmol) and cyanuric chloride (1.0 g, 5.4 mmol) were dissolved in a mixture of 50 mL of 2-butanone, heated to 90 ℃, and stirred 48h in an air atmosphere. After cooling to room temperature, the mixture was poured into 100 mL water and extracted with 50 mL dichloromethane, and the extraction step was repeated three times. The organic layer was collected and washed with water, dried over anhydrous MgSO 4 And (5) drying. The filtrate was evaporated to remove the solvent. Finally, purification by dichloromethane column chromatography gave the triazole triazine triphenyl bromide (TTT-Br) in yield (2.58, g, 60%).
Wherein the structure of the triazole triazine triphenyl bromide is shown in a formula 5:
。
s2, weighing triazole triazine triphenyl bromide (532.9 mg,0.80 mmol) and 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzo [ c ]][1，2，5]Thiadiazole (465.7 mg,1.20 mmol) and 25.0 mg Pd (PPh) 3 ) 4 Dissolving in 35.0 mL DMF, adding K 2 CO 3 (2M，4mL) and then under the nitrogen atmosphere, heating to 120 ℃ to react 5h, heating to 150 ℃ to react 48h. After the completion of the reaction, the reaction mixture was cooled to room temperature.
S3, filtering the reaction mixture, pouring the obtained solid substance into a Buchner funnel, and washing with deionized water, ethanol and acetone in sequence for at least five times. Further purifying 24 h by THF Soxhlet extraction, and vacuum drying at 80 ℃ after extraction is finished to obtain a product TTT-BT (808.9 mg, 81%) based on triazole triazinyl conjugated microporous polymer material, wherein the structure of the TTT-BT is shown as a formula 6:
。
wherein benzo [ c ]][1，2，5]The infrared spectra of thiadiazole (BT), triazolotriazine triphenyl bromide (TTT-Br) and TTT-BT are shown in figure 1, and as can be seen from figure 1, benzo [ c ]][1，2，5]The methyl peak of thiadiazole is 2991 cm -1 There is a characteristic peak present at 1650 cm -1 The peaks of bromine atoms of triazole triazine triphenyl bromide are arranged, so that characteristic peaks of TTT-BT at the positions are weakened, and the positions and the peak intensities of functional groups of the patterns of the monomer and the polymer are combined, so that the successful synthesis of TTT-BT by the polymerization reaction can be determined.
FIG. 2 is a nuclear magnetic hydrogen spectrum of TTT-BT, from which: 1 H NMR (DMSO-d 6 , 400 MHz, ppm): δ 7.98~7.96(d，6H )，7.91~7.89（d，6H）。
FIG. 3 shows electron paramagnetic resonance spectroscopy of TTT-BT, which shows that O is generated within a period of time after DMPO is added 2 •− Thus, a signal peak is shown in the spectrogram, so that the polymer can be determined to generate mainly O under the photocatalysis 2 •− 。
Fig. 4 is a graph of the kinetic decay of TTT-BT after pulse excitation at 485 nm, with an excited state lifetime of up to 30.5 μs clearly seen, with transient absorption under Ar (λem=450 nm) atmosphere.
Example 2 a triazolyltriazinyl based conjugated microporous polymer TTT-Th was prepared.
S1, preparing triazole triazine triphenyl bromide
5- (4-bromophenyl) -2HTetrazole (3.3 g, 14.8 mmol), anhydrous K 2 CO 3 (8.2 g, 59.2 mmol) and cyanuric chloride (1.0 g, 5.4 mmol) were dissolved in a mixture of 50 mL of 2-butanone, heated to 90 ℃, and stirred 48h in an air atmosphere. After cooling to room temperature, the mixture was poured into 100 mL water and extracted with 50 mL dichloromethane, and the extraction step was repeated three times. The organic layer was collected and washed with water, dried over anhydrous MgSO 4 And (5) drying. The filtrate was evaporated to remove the solvent. Purification by dichloromethane column chromatography gave the triazolotriazine triphenyl bromide product (2.58 g, 60%).
S2, triazole triazine triphenyl bromide (532.9 mg,0.80 mmol), 2, 5-bis (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) thiophene (385.4 mg,1.20 mmol) and 25.0 mg Pd (PPh) 3 ） 4 Dissolving in 35.0 mL DMF and adding K 2 CO 3 The (2M, 4 mL) solution was mixed homogeneously, and then was heated to 120℃for reaction 5h under nitrogen, then heated to 150℃for reaction 48h. After the completion of the reaction, the reaction mixture was cooled to room temperature.
S3, filtering the reaction mixture, pouring the obtained solid substance into a Buchner funnel, and washing with deionized water, ethanol and acetone in sequence for at least five times. Further purification 24 h was then performed by soxhlet extraction with THF. After the extraction was completed, the mixture was dried under vacuum at 80℃to obtain TTT-Th (798.8 mg, 86%) as a yellow powder.
Wherein the structure of TTT-Th is shown in formula 7:
。
example 3 a triazolyltriazinyl based conjugated microporous polymer TTT-Ph was prepared.
S1, preparing triazole triazine triphenyl bromide
5- (4-bromophenyl) -2HTetrazole (3.3 g, 14.8 mmol), anhydrous K 2 CO 3 (8.2 g, 59.2 mmol) and cyanuric chloride (1.0 g, 5.4 mmol) were dissolved in a mixture of 50 mL of 2-butanone, heated to 90 ℃, and stirred 48h in an air atmosphere. After cooling to room temperature, the mixture was poured into 100 mL water and extracted with 50 mL dichloromethane, and the extraction step was repeated three times. The organic layer was collected and washed with water, dried over anhydrous MgSO 4 And (5) drying. The filtrate was evaporated to remove the solvent. Then, the triazole triazine triphenyl bromide was purified by dichloromethane column chromatography to give the yield (2.58, g, 60%).
S2, triazole triazine triphenyl bromide 532.9 mg,0.80 mmol), 1, 4-phenylene diboronic acid pinacol diester (396.0 mg,1.20 mmol) and 25.0 mg Pd (PPh) 3 ） 4 Dissolving in 35.0 mL DMF and adding K 2 CO 3 The (2M, 4 mL) solution was in a homogeneously mixed state. Under the nitrogen atmosphere, the mixture is heated to 120 ℃ to react 5h, then the temperature is raised to 150 ℃ to react 48h. After the reaction was completed, the reaction mixture was cooled to room temperature. The reaction mixture was filtered and the resulting solid material was washed with deionized water, ethanol and acetone sequentially, at least five times. Further purification 24 h was then performed with THF soxhlet extraction. After drying in vacuo at 80℃the product was obtained as a yellow powder TTT-Ph (798.8 mg, 86%).
Wherein the structure of TTT-Ph is shown in formula 8:
。
comparative example 1 a conjugated microporous polymer Ph-BT based on benzo [ c ] [1,2,5] thiadiazole (BT) was prepared.
S1, weighing 4, 4-dibromo-5-4-bromophenyl-1, 1:3, 1-terphenyl (434.5 mg,0.80 mmol), 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzo [ c ]][1，2，5]Thiadiazole (465.7 mg,1.20 mmol) and 25.0 mg Pd (PPh) 3 ） 4 Dissolving in 35.0 mL DMF and adding K 2 CO 3 The (2M, 4 mL) solution is in a uniform mixing state, and is heated to 120 ℃ to react 5 and h under the nitrogen atmosphere, then is heated to 150 ℃ to react 48 and h. After the completion of the reaction, the reaction mixture was cooled to room temperature.
S2, filtering the reaction mixture, washing with deionized water, ethanol and acetone in sequence, washing at least five times, and further purifying 24 h by Soxhlet extraction (THF). Vacuum drying at 80deg.C to obtain yellow powder Ph-BT (783.2 mg, 87%) with structural formula shown in formula 9:
。
comparative example 2 a conjugated microporous polymer Tr-BT based on benzo [ c ] [1,2,5] thiadiazole (BT) was prepared.
S1, weighing 2,4, 6-tri (4-bromophenyl) -1,3, 5-triazine (436.8 mg,0.80 mmol), 4, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzo [ c ]][1，2，5]Thiadiazole (465.7 mg,1.20 mmol) and 25.0 mg Pd (PPh) 3 ) 4 Dissolving in 35.0 mL DMF and adding K 2 CO 3 The (2M, 4 mL) solution was mixed homogeneously, and then was heated to 120℃for reaction 5h under nitrogen, then heated to 150℃for reaction 48h. After the completion of the reaction, the reaction mixture was cooled to room temperature.
S2, filtering the reaction mixture, washing with deionized water, ethanol and acetone in sequence, washing at least five times, and further purifying 24 h by Soxhlet extraction (THF). Vacuum drying at 80℃gave Tr-BT (821.3 mg, 91%) as a yellow powder.
Wherein the structure of Tr-BT is shown in formula 10:
。
experimental example 1, the ability of Ph-BT, tr-BT, TTT-Th and TTT-Ph to catalyze uranium ion reduction was examined.
Adding Ph-BT or Tr-BT or TTT-Th or TTT-Ph prepared by 50.0 mg into 50.0 mL 100.0 ppm U (VI) solution (containing 5.0 mL methanol), ultrasonic treating for 2 min, stirring continuously, and mixing with small amount of negligible NaOH (0.1M) or HNO 3 (0.1) M) solution pH was adjusted. The resulting mixture was stirred continuously in the dark before irradiation60 min reaches adsorption-desorption equilibrium. Subsequently, a 300W Xe lamp (light source model: SHX-F300) with a 400 nm cut-off filter was used as a light source. In a given time, a sample aliquot (2.0. 2.0 mL) of the solution was pipetted and filtered through a 0.22 μm nylon filter. And the filtrate was analyzed by inductively coupled plasma mass spectrometry (ICP-MS).
(1) Investigation of degradation efficiency of Ph-BT, tr-BT, TTT-Th and TTT-Ph
Through calculation, the degradation efficiencies of Ph-BT, tr-BT, TTT-Th and TTT-Ph are 31%, 76%, 99%, 95% and 90%, respectively, and compared with non-triazole triazinyl conjugated microporous polymers, the degradation rate of the triazole triazinyl conjugated microporous polymers TTT-BT, TTT-Th and TTT-Ph prepared by the invention on uranium (VI) is obviously increased.
(2) Examine degradation curve graphs of Ph-BT, tr-BT and TTT-BT for extracting uranium from seawater by photocatalysis
At a given time, an aliquot (2 mL) was taken and filtered through a 0.22 μm nylon filter. Determination of UO in supernatant by ICP-MS 2 2+ Content of UO(s) 2 2 + The light reduction efficiency calculation formula of (2) is as follows:
，
wherein RE is the degradation rate of the catalyst; c (C) 0 And C t The concentration of the solution (ppm, mg/L) at the initial and contact times t (min), respectively.
The results are shown in fig. 5, wherein C represents the current concentration at time t, and fig. 5 is a degradation graph of conjugated microporous polymers Ph-BT, tr-BT and TTT-BT for extracting uranium from seawater by photocatalysis, and after the reduction reaction of TTT-BT and uranium (VI) can be obtained by analysis, the degradation efficiency of the conjugated microporous polymers Ph-BT and Tr-BT is found to be almost 99% by calculation, and the degradation efficiency of the conjugated microporous polymers Ph-BT and Tr-BT is not high.
(3) Examining the dynamics curve of Ph-BT, tr-BT and TTT-BT for extracting uranium from seawater by photocatalysis
The three catalysts were each reacted with uranium solution and, at a given time, aliquots (2 mL) were taken and filtered through a 0.22 μm nylon filter. Measurement by ICP-MSUO in supernatant 2 2+ After the degradation efficiency is obtained, the kinetic constant of the material can be obtained by taking the logarithm of the material and then fitting the material. As shown in FIG. 6, the kinetic constant of TTT-BT obtained by analysis was maximized, indicating that it reacted with U (VI) to form UO 2 2+ Fastest.
(4) Examine degradation curve graph of TTT-BT photocatalysis seawater uranium extraction
FIG. 7 is a graph of degradation of TTT-BT in photocatalytic seawater uranium extraction, which can be analyzed to yield a reduction reaction between TTT-BT and uranium (VI), and two groups of TTT-BT react with uranium solution without illumination or catalyst. The calculation mode is consistent with that in (2), and analysis shows that the degradation efficiency of the catalyst under the illumination condition reaches almost 99 percent. And hardly degrades under the condition of no illumination and catalyst TTT-BT.
(5) Investigation of degradation curves of different pH values in TTT-BT photocatalysis seawater uranium extraction
Fig. 8 is a degradation curve of TTT-BT at different pH in the photocatalytic seawater uranium extraction, where the degradation effect is best when we can obtain the ph=6 from the figure by changing the pH difference of the uranium solution to detect when the reduction reaction of TTT-BT and uranium (vi) occurs.
(6) Recovery performance curve graph for examining TTT-BT photocatalysis seawater uranium extraction
After the end of the first reaction, 1M Na was used 2 CO 3 Washing TTT-BT to eliminate UO on surface 2 2+ The washing was repeated five times with deionized water. Then, the mixture was dehydrated in vacuum at 60℃for 8h. And then the dried catalyst reacts with uranium, the steps are repeated for three times, the recovery performance curve of the TTT-BT photocatalysis seawater uranium extraction is shown in the figure 9, the recovery performance of the TTT-BT photocatalysis seawater uranium extraction can be analyzed to obtain the recovery performance of the TTT-BT and the uranium (VI) after the reduction reaction is up to 99 percent after the reaction is carried out, the loss is almost avoided, and the catalyst can be recycled.
(7) Examine the photo-reduction performance diagram of U (VI) in TTT-BT photo-catalytic seawater uranium extraction in the presence of other interfering ions
FIG. 10 is a graph showing the photoreduction performance of U (VI) in TTT-BT photocatalytic seawater uranium extraction in the presence of interfering ions, wherein different ions are added to the reaction solution for reaction, and each set of data in FIG. 10 shows the UO before and after the addition of different interfering ions 2 2+ C/C of (C) 0 The concentration ratio shows that the photocatalytic seawater uranium extraction U (VI) of the TTT-BT has high selectivity on the reduced metal uranium in the presence of interfering ions.
Claims (10)
1. The triazole triazinyl-based conjugated microporous polymer is characterized in that the structural general formula of the polymer is shown as formula 1:
；
wherein R is selected from any one of structures shown in formulas 2-4:
。
2. the conjugated microporous polymer according to claim 1, wherein the conjugated microporous polymer is prepared by the following method:
s1, preparing triazole triazine triphenyl bromide: 5- (4-bromophenyl) -2HTetrazole, anhydrous K 2 CO 3 And cyanuric chloride are dissolved in 2-butanone, heated and stirred in an air atmosphere; after cooling to room temperature, the mixture was poured into water and extracted with dichloromethane; collecting an organic layer, washing, drying and purifying by using dichloromethane column chromatography to obtain triazole triazine triphenyl bromide;
s2, preparing a triazolyl triazinyl conjugated microporous polymer: triazole triazine triphenyl bromide prepared in the step S1, borate compound and K 2 CO 3 、Pd(PPh 3 ) 4 AndN,N-dimethylformamide is mixed, heated in an inert gas atmosphere, and cooled to room temperature after the reaction is finished to obtain a reaction mixture;
and S3, filtering, washing and further purifying the reaction mixture prepared in the step S2 by Soxhlet extraction, and vacuum drying to obtain the triazole triazinyl conjugated microporous polymer material.
3. The conjugated microporous polymer according to claim 2, wherein in step S1, 5- (4-bromobenzene) -2HTetrazole, anhydrous K 2 CO 3 And the mass ratio of the cyanuric chloride is 3-4:8-9:1-1.8.
4. The conjugated microporous polymer according to claim 2, wherein the heating temperature in step S1 is 90 ℃ and the reaction time is 48h; the extraction in the step S1 is repeated three times.
5. The conjugated microporous polymer according to claim 2, wherein in the step S2, the molar ratio of triazole triazine triphenyl bromide to the borate compound is 2-3.1: 3-4.
6. The conjugated microporous polymer according to claim 2, wherein the heating reaction in step S2 is performed by heating to 100-120 ℃ for 5-h, and then heating to 135-155 ℃ for 24-48 hours.
7. The conjugated microporous polymer according to claim 2, wherein the soxhlet extraction time in step S3 is 24 h and the vacuum drying temperature is 80 ℃.
8. Use of the conjugated microporous polymer according to any of claims 1 to 7 as a photocatalyst in uranium reduction, comprising the steps of:
s1, adding a conjugated microporous polymer into uranium (VI) solution, and adjusting the pH value to 6;
and S2, continuously stirring the mixed solution obtained in the step S1 in the dark under the normal-temperature air atmosphere, and then reducing the photocatalytic uranium (VI) into uranium (IV) by using a xenon lamp as a light source.
9. The use according to claim 8, wherein the uranium (VI) solution in the S1 step has a concentration of 50-100 ppm, and the uranium (VI) solution contains 10% by mass of methanol.
10. The use according to claim 8, wherein the duration of stirring in step S2 is 1 h and the power of the xenon lamp is 300W.
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