CN115124726B - For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof - Google Patents

For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof Download PDF

Info

Publication number
CN115124726B
CN115124726B CN202210628980.4A CN202210628980A CN115124726B CN 115124726 B CN115124726 B CN 115124726B CN 202210628980 A CN202210628980 A CN 202210628980A CN 115124726 B CN115124726 B CN 115124726B
Authority
CN
China
Prior art keywords
coordination polymer
porous coordination
photocatalytic
organic
methanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210628980.4A
Other languages
Chinese (zh)
Other versions
CN115124726A (en
Inventor
李风亭
贾焘
顾逸凡
吴江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN202210628980.4A priority Critical patent/CN115124726B/en
Publication of CN115124726A publication Critical patent/CN115124726A/en
Application granted granted Critical
Publication of CN115124726B publication Critical patent/CN115124726B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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]
    • B01J35/39—
    • B01J35/61—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Abstract

The invention provides a method for CO 2 Novel porous coordination polymer subjected to photocatalytic reduction and preparation method thereof, belonging to CO 2 The field of photocatalytic reduction of new materials. Novel porous coordination polymer [ Co ] 2 (TF‑ipa) 2 (dpe) 2 (H 2 O)] n The photocatalyst is prepared from Co (NO) 3 ) 2 ·6H 2 O, organic ligand 1, 2-bis (4-pyridine) ethylene and organic ligand tetrafluoroisophthalic acid are added into an organic solution, and the organic solution is prepared by a low-temperature solvothermal synthesis method. The catalyst prepared by the invention can be used for photocatalytic reduction of CO under simulated sunlight condition 2 Conversion of the resource into gaseous products CO and CH 4 . The porous coordination polymer photocatalyst is used for preparing CO 2 The adsorption performance is strong, the light absorption efficiency is high, the reactive sites are rich, the photocatalytic reduction efficiency is high, and the product selectivity is high; the synthesis is simple, the structure is stable, and the recovery and regeneration are easy; in CO 2 Is utilized by photocatalytic resource conversion and CO 2 The method has important application prospect in the aspects of emission reduction, efficient solar energy utilization and the like.

Description

For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof
Technical Field
The present invention relates to CO 2 The field of new photocatalytic reduction materials, in particular to a catalyst for CO 2 A preparation method of a novel porous coordination polymer through photocatalytic reduction.
Background
Atmospheric carbon dioxide (CO) caused by artificial emissions 2 ) Climate warming caused by the dramatic rise in level is one of the most serious global problems today. Since 1800 years, CO in the atmosphere 2 The concentration has been significantly increased from around 280ppm to 400ppm over 2018. CO 2 The increase in emissions is mainly from the combustion of coal, oil and natural gas. Thus, to reduce CO in the atmosphere 2 While the development of renewable energy technology to achieve more significant changes in energy infrastructure,there is also a need to develop efficient CO 2 Is a technology for capturing and recycling.
In a plurality of COs 2 In the emission reduction technology, CO is reduced by photocatalysis 2 The technology not only can reduce CO in the atmosphere 2 Content, and also CO by solar energy 2 Photocatalytic conversion to valuable chemicals is considered one of the most promising technologies. The porous coordination polymer material, also called metal organic framework material, is a three-dimensional porous material with a periodic network structure, consists of inorganic metal ions (or metal clusters) and organic ligands, has large specific surface area, adjustable structure, abundant catalytic active sites, unique electronic energy band structure, excellent gas adsorption performance and other unique properties, and enables the poly Kong Peiwei polymer material to reduce CO in photocatalysis 2 The resource conversion field has wide prospect.
However, different crystal structures and metal doping are specific to CO 2 The photocatalytic reduction effect of (a) is not the same, for example CN202110817705.2 provides a zero-valent silver-doped silver-based coordination polymer which belongs to the P1 space group of a triclinic system and is a complex of elemental silver and silver-based coordination polymer, and the photocatalytic activity of the zero-valent silver-doped silver-based coordination polymer benefits from Ag 0 The material is suitable for photocatalytic degradation of organic matters such as methyl orange in wastewater under the synergistic effect with silver-based coordination polymer, and the degradation mechanism is based on a composite heterostructure.
CN201710080908.1 discloses a catalyst with visible light catalytic reduction of CO 2 Ruthenium coordination polymer with performance, which belongs to monoclinic C2/C space group, metal ruthenium is rare metal element and is high in price, and mainly uses CO 2 The photocatalytic reduction product is HCOO – . But the preparation process is complex, the reaction temperature is high, the synthesis period is long, and moreover, the reaction process involves HCl and HClO 4 And the acid with equal strong corrosiveness has higher risk and higher synthesis cost.
CN201911033806.X provides a visible light photocatalyst for synthesizing water gas and preparation and application thereof, and discloses a novel cobalt quantum dot supported covalent organic framework polymer (Co@COFs), wherein the photocatalyst is a composite material of Co quantum dots and a covalent organic framework polymer COFs, the Co quantum dots do not participate in coordination with the COFs, the preparation method is complex, the photocatalytic activity benefits from the synergistic effect between the Co quantum dots and the COFs, but a bipyridine ruthenium photosensitizer is added in a photocatalytic system, the bipyridine ruthenium photosensitizer is a common photosensitizer and is expensive, the photocatalytic activity of the photosensitizer can be greatly improved by adding the photosensitizer, and the photocatalytic mechanism is based on a composite heterostructure.
Therefore, development of a low-cost, simple and efficient photocatalytic reduction method for CO is needed 2 A porous coordination polymer material photocatalyst with performance.
Disclosure of Invention
In view of the above problems with the prior art, the present invention provides a method for CO 2 Novel porous coordination polymers of photocatalytic reduction and a process for their preparation. The invention can reduce CO by photocatalysis 2 Conversion of the resource into gaseous products CO and CH 4 For CO 2 The adsorption performance is strong, the light absorption efficiency is high, the reactive sites are rich, the photocatalytic reduction efficiency is high, and the product selectivity is high; the synthesis is simple, the structure is stable, and the recovery and regeneration are easy; in CO 2 Is utilized by photocatalytic resource conversion and CO 2 The method has important application prospect in the aspects of emission reduction, efficient solar energy utilization and the like.
The technical scheme of the invention is as follows:
for CO 2 Novel photocatalytic reduced porous coordination polymers having the chemical formula [ Co ] of crystalline materials 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Wherein Co represents a metallic cobalt center, TF-ipa represents organic ligand tetrafluoroisophthalic acid, and the structural formula is
Figure SMS_1
dpe the organic ligand 1, 2-bis (4-pyridine) ethylene with the structural formula
Figure SMS_2
H 2 O represents a water molecule coordinated with the cobalt Co of the metal center.
Further, the porous coordination polymer belongs to an orthorhombic system, and has a space group of C2 21 and a unit cell parameter of
Figure SMS_3
alpha＝90，beta＝90，gamma＝90。
Further, the porous coordination polymer material is provided with periodic cavities, and fluorine-based negative groups are distributed on the surfaces of the cavities.
The invention also provides a preparation method of the novel porous coordination polymer, which comprises the following steps:
(1) Co (NO) 3 ) 2 ·6H 2 Adding O, organic ligand 1, 2-bis (4-pyridine) ethylene and organic ligand tetrafluoroisophthalic acid into an organic solution, and fully dissolving by ultrasonic oscillation and magnetic stirring; transferring the mixed solution obtained by dissolution into a glass reaction bottle with a screw cap or a polytetrafluoroethylene lining reaction kettle, and heating at 60-80 ℃ for 24-48 h to obtain an orange homogeneous crystal material;
(2) Filtering the obtained homogeneous crystal material, washing unreacted impurities with N, N-dimethylformamide and methanol, and then placing the mixture in methanol for solvent exchange treatment to remove solvent molecules in pore channels of the material;
(3) And (3) placing the obtained material under a vacuum condition with the temperature of 70-120 ℃ and performing activation treatment for 24-48 hours to obtain the novel porous coordination polymer material.
Further, the organic ligand 1, 2-bis (4-pyridine) ethylene, the organic ligand tetrafluoroisophthalic acid and Co (NO) in step (1) 3 ) 2 ·6H 2 The molar ratio of O is 1:0.1 to 10:0.1 to 10.
Further, the organic solvent in the step (1) consists of N, N-dimethylformamide and methanol, wherein the volume ratio of the N, N-dimethylformamide to the methanol is 1:0.1 to 10.
Further, the time of the exchange treatment in the step (2) is 3-5 days, and the methanol is exchanged 2-3 times per day.
Further, the filtering process in the step (3) uses a glass sand core filtering device and an organic phase microporous filter membrane with the pore diameter of 0.2-0.5 mu m for filtering.
The invention further provides application of the porous coordination polymer, which is used for preparing visible light catalytic reduction CO 2 Conversion to gaseous products CO and CH 4 Is a heterogeneous photocatalyst material of (a).
The beneficial technical effects of the invention are as follows:
(1) The tetrafluoroisophthalic acid which is an organic ligand designed and synthesized by the invention is polycarboxylic acid which can be coordinated and extended at two ends, and the other organic ligand 1, 2-bis (4-pyridine) ethylene has 2 pyridine N atoms, can participate in coordination in two directions respectively, and can be self-assembled with the metal cobalt center to form a porous coordination polymer.
The prepared porous coordination polymer [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Two metal cobalt centers are coordinated with the organic coordination, wherein one metal cobalt center is coordinated with four oxygen on the carboxyl of the organic ligand tetrafluoroisophthalic acid, the other metal cobalt center is coordinated with three oxygen on the carboxyl of the organic ligand tetrafluoroisophthalic acid, and a water molecule is coordinated, in addition, each metal cobalt center is coordinated with two nitrogen of the organic ligand 1, 2-bis (4-pyridine) ethylene, so that a three-dimensional staggered three-dimensional structure with zero-dimensional cavities is formed.
(2) The invention provides [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Has unique high pore structure, high specific surface area and CO 2 Adsorption capacity and light absorption capacity, and has rich active sites such as fluorine group and other electronegative groups, which is beneficial to CO 2 The reduction reaction efficiency is improved. In addition, the stability of the material is high, and the thermal decomposition temperature is about 220 ℃.
(3) Compared with the conventional photocatalyst, the novel porous coordination polymer material adopted by the invention has a special crystal structure of orthorhombic system (space group: C2 21), and the material can catalyze CO by photocatalysis 2 Reduction and high selectivity conversion to CO, the main products being CO and CH 4 And is photo-catalyzedThe method has the advantages of high conversion efficiency, excellent performance, repeated regeneration and utilization, simple and safe preparation process operation, high yield and no byproducts.
(4) The invention provides the photocatalytic reduction of CO 2 The method adopts simulated sunlight driving and can be implemented under the environmental condition, has the advantages of simple and mild operation condition, low energy consumption, small equipment investment and the like, and has the function of photocatalysis of CO 2 High conversion efficiency, simple and convenient flow, low energy consumption for material filtering recovery and regeneration, and the like, and is expected to be used in CO 2 Is utilized by photocatalytic resource conversion and CO 2 Has important application prospect in emission reduction.
Drawings
In order to more clearly illustrate the embodiments of the invention and the solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, which are only some embodiments of the invention, from which other drawings can be obtained by a person skilled in the art without the inventive effort.
FIG. 1 shows the [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n X-ray powder diffraction experimental results of (2);
FIG. 2 shows the [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n And the X-ray powder diffraction experimental result after the vacuum activation after the methanol solvent exchange;
FIG. 3 shows the [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Thermal gravimetric curves before and after vacuum activation;
FIG. 4 shows the activated [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n In the photocatalysis of CO 2 CO and CH after 6 hours reduction 4 Yield of (2);
FIG. 5 shows the activated [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n In the photocatalysis of CO 2 CO and CH after 5 hours reduction 4 Yield of (2);
FIG. 6 shows the activated [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n In the photocatalysis of CO 2 The gaseous products CO and CH after 5 hours of reduction 4 Is a gas chromatographic monitoring chart of (2);
FIG. 7 is [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n The space coordination structure diagram is obtained after the crystal material is subjected to single crystal X-ray diffraction test and analysis.
FIG. 8 is [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic reduction of CO by materials 2 Is a schematic representation of the reaction mechanism.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
weigh 109mg Co (NO) 3 ) 2 ·6H 2 O,68mg dpe and 89mg TF-ipa were added to a N, N-dimethylformamide/methanol (1:1, 30 mL) mixture, respectively, and after 5 minutes of sonication a clear solution was obtained, followed by transferring the above solution to a glass reaction flask with a screw cap, heating to 70℃in an oven and holding for 36 hours. After the reaction was completed, the reaction mixture was filtered using a 0.22 μm organic filter membrane, and the precipitate was washed 3 times with 15mL of N, N-dimethylformamide and 15mL of methanol. The resulting material was immersed in methanol and subjected to solvent exchange for 5 days, with 2 changes of methanol per day, each time with 30mL of methanol. Finally, heating to 80 ℃ in a vacuum oven, and activating for 24 hours to obtain activated [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n 。
The material was analyzed by X-ray powder diffraction, and the result was consistent with the powder diffraction obtained by analysis of the structure simulation (as shown in fig. 1), and the powder diffraction of the activated material was consistent with the powder diffraction of the synthesized material (as shown in fig. 2). The thermogravimetric curves of the material before and after vacuum drying (as shown in figure 3) indicate that the material is structurally stable after activation after drying at 80 ℃.
Example 2:
10.9mg Co (NO) 3 ) 2 ·6H 2 O,68mg dpe and 8.9mg TF-ipa were added to N, N-dimethylformamide/methanol (1:0.5, 30 mL) mixed solvent, respectively, and after 5 minutes of sonication a clear solution was obtained, which was then transferred to a glass reaction flask with a screw cap, heated to 60℃in an oven and maintained for 48 hours. After the reaction was completed, the reaction mixture was filtered using a 0.35 μm organic filter membrane, and the precipitate was washed 3 times with 15mL of N, N-dimethylformamide and 15mL of methanol. The resulting material was immersed in methanol and subjected to solvent exchange for 3 days, with 3 methanol changes per day, each time using 30mL of methanol. Finally, heating to 120 ℃ in a vacuum oven, and activating for 24 hours to obtain activated [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n 。
Example 3:
1090mg Co (NO) 3 ) 2 ·6H 2 O,68mg dpe and 890mg TF-ipa were added to a N, N-dimethylformamide/methanol (1:9, 300 mL) mixture, respectively, and after 5 minutes of sonication a clear solution was obtained, which was then transferred to a glass reaction flask with a screw cap, heated to 80℃in an oven and maintained for 24 hours. After the reaction was completed, the reaction mixture was filtered using a 0.5 μm organic filter membrane, and the precipitate was washed 3 times with 15mL of N, N-dimethylformamide and 15mL of methanol. The resulting material was immersed in methanol and subjected to solvent exchange for 4 days, with 2 changes of methanol per day, each time with 30mL of methanol. Finally, heating to 70 ℃ in a vacuum oven, and activating for 48 hours to obtain activated [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n 。
Test example:
the invention relates to the photocatalytic reduction of CO 2 The reaction conditions of (2) are as follows: 50mg of catalyst was magnetically stirred in a 50mL solution containing 30mL of acetonitrile and 10mL of deionized water and 10mL of triethanolamine, and the vessel was a 250mL quartz vessel. Before the reactionWith pure CO 2 The gas is blown into the container for half an hour to eliminate the dissolved oxygen, and then pure CO is stably introduced 2 And (3) gas. Using simulated sunlight (300W Xe lamp, wavelength: 360-800nm, light intensity: 480mW cm) -2 ) As a light source, the temperature of the reactor was maintained at 25 ℃ by circulation of cooling water. The test duration was 5 hours, the sampling was once at 1 hour intervals, and the product was detected by gas chromatography.
Activated [ Co ] of example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Is (are) photocatalytic reduction of CO 2 The reactivity of the gas product CO was evaluated to give a yield of 131.4. Mu. Mol/g (cat) and CH for 6 hours 4 The yield of CO was 29.1. Mu. Mol/g (cat) (as shown in FIG. 4), and the yield of CO was 104.4. Mu. Mol/g (cat) and CH for 5 hours as a gas product 4 The yield of (C) was 27.3. Mu. Mol/g (cat) (see FIGS. 5 and 6).
The illumination time was 1,2, 3 and 4 hours, respectively, [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic CO of materials 2 The reduction properties are summarized in table 1 below:
TABLE 1
Illumination time (hours) CO yield mu mol/g (cat) CH 4 Yield mu mol/g (cat)
1 3.7 9.8
2 14.3 14.9
3 35.8 16.5
4 66.8 22.6
After the photocatalytic reaction is finished, stopping air intake, and carrying out suction filtration on the photocatalyst [ Co ] in the quartz container by using a glass sand core filter device 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Recycling and collecting, and carrying out methanol exchange and vacuum drying activation again to complete the regeneration of the catalyst.
The [ Co ] prepared by the invention 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n The spatial coordination structure obtained by single crystal X-ray diffraction test and analysis of the crystal material is shown in figure 7 [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic reduction of CO by materials 2 The reaction mechanism of (2) is shown in FIG. 8.
Although the embodiments of the present invention have been disclosed in the foregoing description and drawings, it is not limited to the details of the embodiments and examples, but is to be applied to all the fields of application of the present invention, it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.

Claims (6)

1. For CO 2 A photocatalytic reduced porous coordination polymer characterized in that the crystalline material of the porous coordination polymer has the chemical formula [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Wherein Co represents a metallic cobalt center, TF-ipa represents organic ligand tetrafluoroisophthalic acid, and the structural formula is
Figure FDA0004124258030000011
dpe it is an organic ligand 1, 2-bis (4-pyridine) ethylene of the formula +.>
Figure FDA0004124258030000012
H 2 O represents a water molecule coordinated with the cobalt Co in the metal center;
the porous coordination polymer belongs to an orthorhombic system, and the space group: c2 22 1 The unit cell parameters are
Figure FDA0004124258030000013
alpha＝90°，beta＝90°，gamma＝90°；
The porous coordination polymer material is provided with periodic pore cavities, and fluorine-based negative groups are distributed on the surfaces of the pore cavities.
2. The method for preparing a porous coordination polymer according to claim 1, comprising the steps of:
(1) Co (NO) 3 ) 2 ·6H 2 Adding O, organic ligand 1, 2-bis (4-pyridine) ethylene and organic ligand tetrafluoroisophthalic acid into an organic solution, and fully dissolving by ultrasonic oscillation and magnetic stirring; transferring the mixed solution obtained by dissolution into a glass reaction bottle with a screw cap or a polytetrafluoroethylene lining reaction kettle, and heating at 60-80 ℃ for 24-48 h to obtain an orange homogeneous crystal material;
(2) Filtering the obtained homogeneous crystal material, washing unreacted impurities with N, N-dimethylformamide and methanol, and then placing the mixture in methanol for solvent exchange treatment to remove solvent molecules in pore channels of the material;
(3) Placing the obtained material under a vacuum condition with the temperature of 70-120 ℃ and performing activation treatment for 24-48 hours to obtain the porous coordination polymer material;
the organic ligands 1, 2-bis (4-pyridine) ethylene, the organic ligands tetrafluoroisophthalic acid and Co (NO) in step (1) 3 ) 2 ·6H 2 The molar ratio of O is 1:0.1 to 10:0.1 to 10.
3. The method according to claim 2, wherein the organic solution in step (1) consists of N, N-dimethylformamide and methanol, and the volume ratio of the N, N-dimethylformamide to the methanol is 1:0.1 to 10.
4. The method according to claim 2, wherein the time of the exchange treatment in step (2) is 3 to 5 days, and methanol is exchanged 2 to 3 times per day.
5. The method according to claim 2, wherein the filtration process in step (2) is performed using a glass sand core filtration device and an organic phase microporous filter membrane having a pore size of 0.2 to 0.5 μm.
6. Use of a porous coordination polymer according to claim 1, characterized in that: the porous coordination polymer is used for preparing visible light catalytic reduction CO 2 Conversion to gaseous products CO and CH 4 Is a heterogeneous photocatalyst material of (a).
CN202210628980.4A 2022-06-06 2022-06-06 For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof Active CN115124726B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210628980.4A CN115124726B (en) 2022-06-06 2022-06-06 For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210628980.4A CN115124726B (en) 2022-06-06 2022-06-06 For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115124726A CN115124726A (en) 2022-09-30
CN115124726B true CN115124726B (en) 2023-05-23

Family

ID=83378018

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210628980.4A Active CN115124726B (en) 2022-06-06 2022-06-06 For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115124726B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734718B (en) * 2018-11-29 2021-02-26 同济大学 Polycarboxylic acid organic ligand based on NDHPI modification and synthetic method
CN109575594A (en) * 2018-12-01 2019-04-05 庄明磊 A kind of new-energy automobile power battery refractory material and preparation method thereof

Also Published As

Publication number Publication date
CN115124726A (en) 2022-09-30

Similar Documents

Publication Publication Date Title
Meng et al. Construction of g-C3N4/ZIF-67 photocatalyst with enhanced photocatalytic CO2 reduction activity
CN107308990B (en) TiO22Preparation method of porphyrin/MOFs ultrathin heteroplasmon
CN111303445B (en) Cobalt-based metal organic framework material and application
CN109201115B (en) Photocatalytic hydrogen production catalyst and preparation method and application thereof
CN106732796B (en) A kind of efficiently reduction CO2Covalent organic polymer visible-light photocatalyst
CN113318787B (en) Catalyst for in-situ growth of MOF on metal substrate and preparation method and application thereof
CN111013608A (en) Metallic nickel modified sulfur indium zinc photocatalyst and preparation method and application thereof
CN111203234B (en) CdIn2S4Nanoblock/SnIn4S8Preparation method of difunctional composite photocatalyst with sheet stacking structure
CN110229347B (en) Metal chelated double-hole covalent organic framework material and preparation and application thereof
CN113058601B (en) Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting
CN111393663B (en) Perylene bisimide base coordination polymer, preparation method and application thereof
CN108906125B (en) Three dish alkene polymer DTP/ zinc-cadmium sulfide Cd of one kind0.5Zn0.5The preparation method of S composite photo-catalyst
Yin et al. Enhanced charge transfer and photocatalytic carbon dioxide reduction of copper sulphide@ cerium dioxide pn heterojunction hollow cubes
CN113231101A (en) Preparation and application of Cu-NM-101(Fe) photocatalyst
CN109331884B (en) Composite hydrogen production catalyst and preparation method and application thereof
CN115124726B (en) For CO 2 Photocatalytic reduced porous coordination polymer and preparation method thereof
CN108080028B (en) Preparation method of 8-hydroxyquinoline iron organic dye photodegradation catalyst
CN116120505A (en) Halogen-containing pyrenyl covalent organic framework polymer photocatalyst, and preparation method and application thereof
CN113398968B (en) MOF-derived TiO 2 Porous g-C 3 N 4 Composite photocatalyst, preparation method and application thereof
CN111793218B (en) Preparation method and application of Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material
CN115069270A (en) CuSAP/CdS photolysis water hydrogen production catalyst and preparation method thereof
CN114887661A (en) Preparation method and application of Ti-based porphyrin material
CN114570429A (en) Monoatomic-supported covalent organic framework material, preparation thereof and application thereof in hydrogen production by photolysis of water
CN116422378B (en) Cu (copper) alloy 2 O-CuXbpy composite material CO 2 Preparation method and application of photoreduction catalyst
CN114621457B (en) Modified iron-based metal organic framework material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Li Fengting

Inventor after: Jia Dao

Inventor after: Gu Yifan

Inventor before: Li Fengting

Inventor before: Jia Dao

Inventor before: Gu Yifan

Inventor before: Wu Jiang