CN107694606A - The covalent triazine ring pyridine framework catalyst and preparation method and application of rhenium modification - Google Patents
The covalent triazine ring pyridine framework catalyst and preparation method and application of rhenium modification Download PDFInfo
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- CN107694606A CN107694606A CN201711057725.4A CN201711057725A CN107694606A CN 107694606 A CN107694606 A CN 107694606A CN 201711057725 A CN201711057725 A CN 201711057725A CN 107694606 A CN107694606 A CN 107694606A
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- catalyst
- triazine ring
- rhenium
- covalent triazine
- modification
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 230000004048 modification Effects 0.000 title claims abstract description 21
- 238000012986 modification Methods 0.000 title claims abstract description 21
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 21
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- XNPMXMIWHVZGMJ-UHFFFAOYSA-N pyridine-2,6-dicarbonitrile Chemical class N#CC1=CC=CC(C#N)=N1 XNPMXMIWHVZGMJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001570 ionothermal synthesis Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 150000003282 rhenium compounds Chemical class 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000008033 biological extinction Effects 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to photocatalysis field, and in particular to the covalent triazine ring pyridine framework catalyst of rhenium modification, and its preparation method and application.Covalent triazine frame material has good adsorption capacity to CO2.Rhenium compound also has certain application in photocatalysis carbon dioxide reduction field.The two is combined using suitable means, CO2 concentration near catalyst can be increased by being enriched with CO2, CO2 is effectively converted into the CO product useful to the mankind by and can.Covalent triazine ring frame material (CTF py) containing pyridine is combined by we with rhenium compound, to be efficiently clean energy resource CO by CO2 photo catalytic reductions.Catalyst in the present invention has wide area extinction (ABSORPTION EDGE is more than 800nm) and high CO2 absorption simultaneously, and the two coordinative role makes catalyst show high photocatalysis efficiency.Catalyst in the present invention compared with the catalyst of other rhenium-containings, in solid and gas system using and solve the problems, such as that cyclicity is bad.
Description
Technical field
The invention belongs to photocatalysis field, and in particular to the covalent triazine ring pyridine framework catalyst of rhenium modification, and its system
Preparation Method and application.
Background technology
Solar energy is considered as one of important new energy.Sunshine is directly absorbed using material can be with so as to carry out reaction
It is effective to utilize the consumption of solar energy and reduction to non-renewable energy resources such as fossil fuels.CO2Photo catalytic reduction reaction can not only
Reacted using solar energy, and can be by CO2Valuable industrial chemicals is converted into, and then mitigates CO2Temperature caused by discharge
Room effect, alleviate the environmental problems such as global warming, disruption of ecological balance.
Covalent triazine frame material, because it has bigger serface, high thermodynamic stability, high chemical stability and enriches
Nitrogen content, show excellent application prospect in fields such as gas storage/separation, catalysis.And to CO2There is good absorption
Ability.Rhenium compound also has certain application in photocatalysis carbon dioxide reduction field.
Covalent triazine ring frame material (CTF-py) containing pyridine is combined by we with rhenium compound, efficiently to incite somebody to action
CO2Photo catalytic reduction is clean energy resource CO.
The content of the invention
The present invention is that have high stability, high CO to obtain one kind2Adsorption capacity, high photocatalysis CO2Reduction efficiency, it is good
Good circulative photochemical catalyst.
The purpose of the present invention can be achieved through the following technical solutions：
First, it is that monomer prepares covalent triazine ring pyridine frame material with 2,6- dicyanopyridines by " ionothermal synthesis ".
Then, by the method for rear modification by Re (CO)5Cl is carried on covalent triazine ring pyridine framework.Comprise the following steps that：
(1) preparation of covalent triazine ring pyridine frame material：In glove box, by 100mg~300mg2,6- dicyanos
Pyridine is sufficiently mixed with 1g~3g anhydrous zinc chlorides.Said mixture is put into quartz ampoule, is vacuumized, tube sealing.In Muffle furnace,
The quartz ampoule equipped with mixture is calcined 1~30 hour in 400 DEG C, is then calcined 1~30 hour in 600 DEG C.After cooling, take out
Solid in pipe, grinding obtain black solid powder, with 0.01-2mol/L salt acid soak 12~48 hours, then use deionization
Neutrality is washed to, it is then continuous to use ethanol, acetone, tetrahydrofuran cleaning 1~5 time, obtain covalent triazine ring pyridine frame material.
(2) preparation of the covalent triazine ring pyridine framework catalyst of rhenium modification：By 50~200mg covalent triazine ring pyridine frames
Frame material, 100~400mgRe (CO)5Cl is added in 50~100mL methanol solution, is added in the environment of 75 DEG C to 90 DEG C
Heat backflow 1~3 day.Afterwards with 10000 rpms of centrifugation 3~10 minutes, continuously with methanol, ethanol, acetone cleaning 1
~5 times, obtain the covalent triazine ring pyridine framework catalyst of rhenium modification.
In the present invention, tell that catalyst material made from method is used to photocatalysis CO2Reduction.
In the present invention, photocatalysis CO2The step of reduction is：
(1) in solid-liquid system, the covalent triazine ring pyridine framework catalyst material of 5~10mg rhenium modification is added, so
1~50mL triethanolamines and acetonitrile mixed solution (volume ratio 0.1~1) are added afterwards.Then vacuumize, be filled with CO2, repeatedly 1~6
It is secondary, then set to 0~3 hours in no light condition decentralization.Afterwards, by device be placed under the irradiation of all band lamp carry out photocatalysis it is anti-
Should, took CO to be detected every 0.1~4 hour.
(2) in solid and gas system, the covalent triazine ring pyridine framework catalyst material that 1~10mg rhenium is modified uniformly is divided
It is dispersed on quartzy filter membrane, then adds 1~5mL triethanolamines and acetonitrile mixed solution (volume ratio 0.1~1), vacuumize, fill
Enter CO2, 1~6 time repeatedly, then set to 0~3 hours in no light condition decentralization.Afterwards, device is placed under the irradiation of all band lamp
Light-catalyzed reaction is carried out, took CO to be detected every 0.1~4 hour.
Compared with prior art, the present invention has advantages below：
(1) catalyst in the present invention has very high specific surface area, can expose substantial amounts of catalytic active center, improves
Light-catalyzed reaction activity.
(2) catalyst in the present invention has very high heat endurance and chemical stability.
(3) catalyst in the present invention has wide area extinction (ABSORPTION EDGE is more than 800nm) and high CO simultaneously2Absorption, the two
Coordinative role makes catalyst show high photocatalysis efficiency.
(4) preparation method of the present invention is simple, workable, has very strong application prospect.
(5) catalyst in the present invention is compared with the catalyst of other rhenium-containings, in solid and gas system using and solve and follow
The problem of ring is bad.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the covalent triazine ring pyridine framework catalyst of rhenium modification prepared by embodiment 1.
Fig. 2 is the CO of the covalent triazine ring pyridine framework catalyst of rhenium modification prepared by embodiment 12Adsorption isotherm.
The covalent triazine ring pyridine framework catalyst for the rhenium modification that Fig. 3 is prepared for embodiment 3 is in solid and gas system to CO2's
Photo catalytic reduction design sketch.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
(1) preparation of covalent triazine ring pyridine frame material：First by raw material 129mg2,6- dicyanopyridines at 75 DEG C
Dried 12 hours in vacuum drying chamber.Then in glove box, by grinding 2,6- dicyanopyridines and the anhydrous chlorine of 1.363g
Change zinc to be sufficiently mixed.Said mixture is put into internal diameter 12mm external diameter 14mm length 20cm quartz ampoules, is vacuumized, tube sealing.In horse
Not in stove, the quartz ampoule that mixture should be housed is calcined 20 hours in 400 DEG C, is then calcined 20 hours in 600 DEG C.After cooling, take
Solid in outlet pipe, grinding obtain black solid powder, with 1mol/L salt acid soak 48 hours, are then washed with deionized water into
Property, ethanol continuously then is used, acetone, tetrahydrofuran cleans 3 times, obtains covalent triazine ring pyridine frame material.
(2) preparation of the covalent triazine ring pyridine frame material of rhenium modification：By 100mg covalent triazine ring pyridine framework materials
Material, 200mgRe (CO)5Cl is added in 100mL methanol solution, is heated to reflux in the environment of 75 DEG C to 90 DEG C 1~3 day.
Afterwards with 10000~12000 rpms of centrifugation 3~10 minutes, continuously cleaned 1~5 time with methanol, ethanol, acetone,
Obtain the covalent triazine ring pyridine frame material of rhenium modification.
Coordination phase is passed through with covalent triazine ring pyridine frame material by rhenium compound in Fig. 1 IR Characterization catalyst
With reference to.Pass through Fig. 2 CO2Adsorption isotherm shows catalyst to CO2With very high adsorbance, enrichment CO can be produced2Effect
Fruit.
Embodiment 2：
In solid-liquid system, the covalent triazine ring pyridine framework catalyst material of 5mg rhenium modification is added, is then added
20mL triethanolamines and acetonitrile mixed solution (volume ratio 0.33).Then vacuumize, be filled with CO2, 3 times repeatedly, then unglazed
Under the conditions of place 2 hours.Afterwards, device is placed under the irradiation of all band lamp and carries out light-catalyzed reaction, took CO to enter every 1 hour
Row detection.
Embodiment 3：
In solid and gas system, the covalent triazine ring pyridine framework catalyst material that 2mg rhenium is modified is dispersed in stone
On English filter membrane, 2mL triethanolamines and acetonitrile mixed solution (volume ratio 0.25) are then added, vacuumizes, is filled with CO2, repeatedly 3
It is secondary, then placed 2 hours under no light condition.Afterwards, device is placed under the irradiation of all band lamp and carries out light-catalyzed reaction, often
CO was taken to be detected every 1 hour.
This catalyst has good photocatalysis efficiency in solid and gas system as seen in Figure 3.By 10 small time
Irradiation catalytic rate is not decayed.
The description of above-described embodiment is for convenience of being understood that in those skilled in the art and using the present invention.
Those skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment, without by creative work.Therefore, the invention is not restricted to embodiment here.
Those skilled in that art according to the present invention, the improvement and modification made to the present invention all should protection scope of the present invention it
It is interior.
Claims (3)
1. the covalent triazine ring pyridine framework catalyst of rhenium modification, by " ionothermal synthesis ", with 2,6- dicyanopyridines for monomer
Covalent triazine ring pyridine frame material is prepared, it is then, by the method for rear modification that rhenium-containing is compound loaded in covalent triazine ring
Catalyst is obtained on pyridine framework, wherein being preferably Re (CO) containing rhenium compound5Cl。
2. a kind of preparation method of the covalent triazine ring pyridine framework catalyst of the rhenium modification described in claim 1, its feature is such as
Under：By 50~200mg covalent triazine ring pyridine frame materials, 100~400mgRe (CO)5Cl is added to 50~100mL methanol
In solution, it is heated to reflux in the environment of 75 DEG C to 90 DEG C 1~3 day, afterwards with 10000 rpms of centrifugation 3~10
Minute, continuously cleaned 1~5 time with methanol, ethanol, acetone, obtain the covalent triazine ring pyridine frame material of rhenium modification.
3. a kind of covalent triazine ring pyridine framework catalyst of the rhenium modification described in claim 1 is used for photo catalytic reduction CO2。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711057725.4A CN107694606A (en) | 2017-11-01 | 2017-11-01 | The covalent triazine ring pyridine framework catalyst and preparation method and application of rhenium modification |
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| CN201711057725.4A CN107694606A (en) | 2017-11-01 | 2017-11-01 | The covalent triazine ring pyridine framework catalyst and preparation method and application of rhenium modification |
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| CN201711057725.4A Pending CN107694606A (en) | 2017-11-01 | 2017-11-01 | The covalent triazine ring pyridine framework catalyst and preparation method and application of rhenium modification |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022217521A1 (en) * | 2021-04-14 | 2022-10-20 | 苏州大学 | Covalent bond-linked tio2@ctf‑py heterojunction material, and preparation method therefor and application thereof |
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2017
- 2017-11-01 CN CN201711057725.4A patent/CN107694606A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022217521A1 (en) * | 2021-04-14 | 2022-10-20 | 苏州大学 | Covalent bond-linked tio2@ctf‑py heterojunction material, and preparation method therefor and application thereof |
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