CN115124726A - For CO 2 Novel porous coordination polymer for photocatalytic reduction and preparation method thereof - Google Patents

For CO 2 Novel porous coordination polymer for photocatalytic reduction and preparation method thereof Download PDF

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CN115124726A
CN115124726A CN202210628980.4A CN202210628980A CN115124726A CN 115124726 A CN115124726 A CN 115124726A CN 202210628980 A CN202210628980 A CN 202210628980A CN 115124726 A CN115124726 A CN 115124726A
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李风亭
贾焘
顾逸凡
吴江
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Tongji University
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Abstract

The invention provides a method for preparing CO 2 A novel porous coordination polymer for photocatalytic reduction and a preparation method thereof, belonging to CO 2 The field of photocatalytic reduction new materials. The novel porous coordination polymer [ Co 2 (TF‑ipa) 2 (dpe) 2 (H 2 O)] n The photocatalyst consists of Co (NO) 3 ) 2 ·6H 2 O, organic ligand 1, 2-bis (4-pyridine) ethylene and organic ligand tetrafluoro mAdding phthalic acid into organic solution, and preparing the compound 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 Resource conversion into gaseous products CO and CH 4 . The porous coordination polymer photocatalyst is used for CO 2 The adsorption performance is strong, the light absorption efficiency is high, the reaction active 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 Photocatalytic resource conversion and utilization and CO 2 Has important application prospect in the aspects of emission reduction, high-efficiency utilization of solar energy and the like.

Description

For CO 2 Novel porous coordination polymer for photocatalytic reduction and preparation method thereof
Technical Field
The invention relates to CO 2 The field of new photocatalytic reduction materials, in particular to a method for preparing a catalyst for CO 2 A preparation method of a novel porous coordination polymer by photocatalytic reduction.
Background
Atmospheric carbon dioxide (CO) caused by artificial emissions 2 ) The climate warming caused by the steep rise in levels is one of the most serious global problems today. Atmospheric CO since 1800 years 2 The concentration has increased significantly from around 280ppm to over 400ppm in 2018. CO 2 2 The increase in emissions is mainly from the combustion of coal, oil and natural gas. Therefore, to reduce atmospheric CO 2 While developing renewable energy technologies to achieve more significant changes in energy infrastructure, there is also a need to develop effective CO 2 The trapping and resource transformation technology.
In a plurality of CO 2 In the emission reduction technology, CO is reduced by photocatalysis 2 The technology can not only reduce CO in the atmosphere 2 Content, and CO can be generated by solar energy 2 The photocatalytic conversion of valuable chemicals is considered to be one of the most promising technologies. The porous coordination polymer material is a three-dimensional porous material with a periodic network structure, consists of inorganic metal ions (or metal clusters) and organic ligands, has the unique properties of large specific surface area, adjustable structure, abundant catalytic active sites, unique electronic energy band structure, excellent gas adsorption performance and the like, and can be used for reducing CO in a photocatalytic manner 2 Has wide prospect in the field of resource transformation.
However, different crystal structures and metal doping for CO 2 The photocatalytic reduction effect of (A) is different, such as CN202110817705.2 provides a zero-valent silver-doped silver-based coordination polymer, which belongs to the P1 space group of the triclinic system, and the zero-valent silver-doped silver-based coordination polymer is a compound of simple substance silver and silver-based coordination polymer, and the photocatalytic activity of the zero-valent silver-doped silver-based coordination polymer is benefited by Ag 0 The material is suitable for photocatalytic degradation of organic matters in wastewater, such as methyl orange, and the degradation mechanism of the material is based on a composite heterostructure due to the synergistic effect of the silver-based coordination polymer and the silver-based coordination polymer.
CN201710080908.1 discloses a method for reducing CO by visible light catalysis 2 The functional ruthenium coordination polymer belongs to a monoclinic system C2/C space group, the metal ruthenium is a rare metal element which is expensive, and the CO is mainly used 2 The photocatalytic reduction product is HCOO – . But the preparation process is complex, the reaction temperature is high, the synthesis period is long, and in addition, the reaction process involves HCl and HClO 4 And the like, the dangerousness is higher, and the synthesis cost is higher.
CN201911033806.X provides a visible light photocatalyst for synthesizing water gas and preparation and application thereof, and discloses a cobalt quantum dot loaded novel covalent organic framework polymer (Co @ COFs), the photocatalyst is a composite material of Co quantum dots and 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 of the photocatalyst is benefited by the synergistic effect between the Co quantum dots and the COFs, a bipyridyl ruthenium photosensitizer is added into a photocatalytic system of the photocatalyst, the photosensitizer is a common photosensitizer and is expensive, the photocatalytic activity of the photocatalyst can be greatly improved by adding the photosensitizer, and the photocatalytic mechanism of the photosensitizer is based on a composite heterostructure.
Therefore, it is urgently needed to develop a photocatalytic reduction method for CO with low cost, simple preparation and high efficiency 2 A porous coordination polymer material photocatalyst with the performance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for CO 2 A novel porous coordination polymer for photocatalytic reduction and a preparation method thereof. The invention can reduce CO by photocatalysis 2 Resource conversion into gaseous products CO and CH 4 To CO 2 The adsorption performance is strong, the light absorption efficiency is high, the reaction active 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 The photocatalysis resource conversion and utilization and CO 2 Has important application prospect in the aspects of emission reduction, high-efficiency utilization of solar energy and the like.
The technical scheme of the invention is as follows:
for CO 2 A novel porous coordination polymer for photocatalytic reduction, the crystalline material of said porous coordination polymer having the chemical formula [ Co 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Wherein Co represents a metal cobalt center, TF-ipa represents an organic ligand tetrafluoro isophthalic acid, and the structural formula is
Figure BDA0003678762620000021
dpe represents organic ligand 1, 2-bis (4-pyridine) ethylene, and its structural formula is
Figure BDA0003678762620000031
H 2 O represents a water molecule coordinated to the metallic center cobalt Co.
Further, the porous coordination polymer belongs to an orthorhombic system, the space group is C2221, the unit cell parameter is
Figure BDA0003678762620000032
alpha＝90，beta＝90，gamma＝90。
Furthermore, 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) mixing Co (NO) 3 ) 2 ·6H 2 Adding O, organic ligand 1, 2-bis (4-pyridine) ethylene and organic ligand tetrafluoro isophthalic acid into an organic solution, and fully dissolving by ultrasonic oscillation and magnetic stirring; transferring the mixed solution obtained by dissolving the above components to a glass reaction vessel with a screw cap or a polytetrafluoroethylene linerHeating the mixture in a reaction kettle at the temperature of between 60 and 80 ℃ for 24 to 48 hours to obtain an orange homogeneous phase crystal material;
(2) filtering the obtained homogeneous phase crystal material, washing unreacted impurities by using N, N-dimethylformamide and methanol, and then placing the material in the 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 at the temperature of 70-120 ℃, and performing activation treatment for 24-48 h to obtain the novel porous coordination polymer material.
Further, the organic ligand 1, 2-bis (4-pyridine) ethylene, the organic ligand tetrafluoro isophthalic acid and Co (NO) in the step (1) 3 ) 2 ·6H 2 The molar ratio of O is 1: 0.1-10: 0.1 to 10.
Further, in the step (1), the organic solvent is composed of N, N-dimethylformamide and methanol, and 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 to 5 days, and the methanol is replaced for 2 to 3 times every day.
Further, in the filtering process in the step (3), a glass sand core filtering device and an organic phase microporous filtering membrane with the aperture of 0.2-0.5 mu m are used for filtering.
The invention further provides application of the porous coordination polymer, and the porous coordination polymer is used for preparing visible light catalytic reduction CO 2 Conversion to gaseous products CO and CH 4 The heterogeneous photocatalyst material of (1).
The beneficial technical effects of the invention are as follows:
(1) the organic ligand tetrafluoro isophthalic acid designed and synthesized by the invention is a polycarboxylic acid which can be coordinately 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 a metal cobalt center to form a porous coordination polymer.
Preparation of the obtained porous coordination Polymer [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Two metal cobalt centers are coordinated with organic coordination, wherein one metal cobalt center is coordinated with four oxygens on a carboxyl group of an organic ligand tetrafluoro-isophthalic acid, the other metal cobalt center is coordinated with three oxygens on a carboxyl group of an organic ligand tetrafluoro-isophthalic acid, and is also coordinated with a water molecule, and each metal cobalt center is coordinated with two nitrogens of an organic ligand 1, 2-bis (4-pyridine) ethylene to form a three-dimensional staggered three-dimensional structure with zero-dimensional pore cavities.
(2) [ Co ] provided by the present invention 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Has unique high-porosity structure, high specific surface area and CO 2 Adsorption capacity and light absorption capacity, and has rich active sites such as fluorine-based isoelectric negative groups, which is beneficial to CO 2 The efficiency of the reduction reaction 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 an orthorhombic system (space group: C2221), and the material can be used for photocatalysis of CO 2 Reducing and converting into CO with high selectivity, wherein the main products are CO and CH 4 And the photocatalytic reduction has the advantages of high conversion efficiency, excellent performance and repeated regeneration and utilization, and the preparation process is simple, convenient and safe to operate, high in yield and basically free of byproducts.
(4) The invention provides a method for photocatalytic reduction of CO 2 The method adopts the simulated sunlight drive 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 photocatalysis CO 2 High conversion efficiency, simple process, low energy consumption for filtering, recovering and regenerating materials and the like, and is expected to be applied to CO 2 The photocatalysis resource conversion and utilization and CO 2 Has important application prospect in emission reduction.
Drawings
In order to more clearly illustrate the embodiments of the present invention and the solutions of the prior art, the drawings needed for describing the embodiments or the prior art will be briefly described below, the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts.
FIG. 1 shows [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n The results of the X-ray powder diffraction experiment of (1);
FIG. 2 shows [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n And the experimental result of X-ray powder diffraction after methanol solvent exchange and vacuum activation;
FIG. 3 shows [ Co ] obtained in example 1 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Thermogravimetric 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 Reduction of CO and CH after 6 hours 4 The yield of (a);
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 Reduction of CO and CH after 5 hours 4 The yield of (a);
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 After 5 hours of reduction the gaseous products CO and CH 4 Gas chromatography monitoring graph of (a);
FIG. 7 is [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n The space coordination structure schematic diagram is obtained after the crystal material is tested and analyzed through single crystal X-ray diffraction.
FIG. 8 shows [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic reduction of CO by materials 2 Schematic diagram of the reaction mechanism of (1).
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
weigh 109mg Co (NO) 3 ) 2 ·6H 2 O, 68mg of dpe and 89mg of TF-ipa were added to a mixed solvent of N, N-dimethylformamide/methanol (1:1, 30mL), respectively, and a clear solution was obtained after 5min of sonication, and then the above solution was transferred to a glass reaction flask with a screw cap, heated to 70 ℃ in an oven and held for 36 hours. After the reaction was completed, the mixture was filtered through a 0.22 μm organic filter, and the precipitate was washed 3 times with 15mL of N, N-dimethylformamide and 15mL of methanol. The resulting material was soaked in methanol for 5 days of solvent exchange, with 2 methanol changes per day, using 30mL of methanol each time. Finally heating to 80 ℃ in a vacuum oven, and activating for 24h 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 results were consistent with the powder diffraction obtained by the analytical 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 (as shown in fig. 3) of the material before and after vacuum drying show that the structure of the material after activation is stable after drying at 80 ℃.
Example 2:
weigh 10.9mg Co (NO) 3 ) 2 ·6H 2 O, 68mg of dpe and 8.9mg of TF-ipa were added to a mixed solvent of N, N-dimethylformamide/methanol (1:0.5, 30mL), respectively, and a clear solution was obtained after 5min of sonication, and then the above solution was transferred to a glass reaction flask with a screw cap, heated to 60 ℃ in an oven and kept for 48 h. After the reaction was completed, the mixture was filtered through a 0.35 μm organic filter, and the precipitate was washed 3 times with 15mL of N, N-dimethylformamide and 15mL of methanol. The material obtained was soaked in methanol for 3 days of solvent exchange, with 3 methanol changes per day, using 30mL of methanol each time. 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 of Co (NO) are weighed 3 ) 2 ·6H 2 O, 68mg of dpe and 890mg of TF-ipa were added to a mixed solvent of N, N-dimethylformamide/methanol (1:9, 300mL), respectively, and a clear solution was obtained after 5min of sonication, and then the above solution was transferred to a glass reaction flask with a screw cap, heated to 80 ℃ in an oven and kept for 24 h. After the reaction was completed, the mixture was filtered through a 0.5 μm organic filter, and the precipitate was washed 3 times with 15mL of N, N-dimethylformamide and 15mL of methanol. The resulting material was soaked in methanol for 4 days of solvent exchange, with 2 methanol changes per day, using 30mL of methanol each time. Finally heating to 70 ℃ in a vacuum oven, and activating for 48h 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 (A) are as follows: 50mg of catalyst was magnetically stirred in a 50mL solution containing 30mL acetonitrile, 10mL deionized water and 10mL triethanolamine in a 250mL quartz container. With pure CO before the reaction 2 Blowing gas into the container for half an hour to eliminate dissolved oxygen, and then stably introducing pure CO 2 A gas. Simulated sunlight (300W Xe lamp, wavelength: 360-800nm, light intensity: 480mW cm) was used -2 ) As a light source, the temperature of the reactor was maintained at 25 ℃ by circulating cooling water. The test duration was 5 hours, the sampling interval was 1 hour, and the product was checked by gas chromatography.
Activated [ Co ] of example 1 according to the above method 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic reduction of CO 2 The yield of gaseous products CO was found to be 131.4. mu. mol/g (cat) and CH at 6 hours 4 The yield of (A) was 29.1. mu. mol/g (cat) (as shown in FIG. 4), and the yield of CO was measured as 104.4. mu. mol/g (cat) and CH as a gaseous product at 5 hours 4 The yield of (a) was 27.3. mu. mol/g (cat) (as shown in FIGS. 5 and 6).
The illumination time is 1,2, 3 and 4 hours respectivelyOf (Co) is present 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic CO of materials 2 The reduction performance is summarized in table 1 below:
TABLE 1
Time of illumination (hours) CO yield μmol/g (cat) CH 4 Yield μmol/g (cat)
1 3.7 9.8
2 14.3 14.9
3 35.8 16.5
4 66.8 22.6
Stopping air intake after the photocatalytic reaction is finished, and performing suction filtration on the photocatalyst Co in the quartz container by using a glass sand core filtering device 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Recovering and collecting, and regenerating the catalyst by methanol exchange and vacuum drying activation.
[ Co ] prepared by the invention 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n The space coordination structure of the crystal material obtained by single crystal X-ray diffraction test and analysis is shown in FIG. 7, [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Photocatalytic reduction of CO by materials 2 The reaction mechanism of (3) is shown in FIG. 8.
While the embodiments of the present invention have been disclosed above, it is not limited to the applications listed in the description and embodiments, but is fully applicable to various fields suitable for the present invention, and it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principle and spirit of the present invention, and therefore the present invention is not limited to the specific details without departing from the general concept defined in the claims and the scope of equivalents thereof.

Claims (9)

1. For CO 2 A novel porous coordination polymer for photocatalytic reduction, characterized in that the chemical formula of the crystalline material of the porous coordination polymer is [ Co ] 2 (TF-ipa) 2 (dpe) 2 (H 2 O)] n Wherein Co represents a metal cobalt center, TF-ipa represents an organic ligand, tetrafluoroisophthalic acid, and the structural formula is shown in the specification
Figure FDA0003678762610000011
dpe represents organic ligand 1, 2-bis (4-pyridine) ethylene, and its structural formula is
Figure FDA0003678762610000012
H 2 O represents a water molecule coordinated to the metallic center cobalt Co.
2. The novel porous coordination polymer according to claim 1, wherein said porous coordination polymer belongs to the orthorhombic system, space group C2221, unit cell parameter is
Figure FDA0003678762610000013
Figure FDA0003678762610000014
alpha＝90，beta＝90，gamma＝90。
3. The novel porous coordination polymer according to claim 1, characterized in that said porous coordination polymer material has periodic cavities with fluorine-based negative groups distributed on the surface.
4. A method for preparing a novel porous coordination polymer according to any of claims 1 to 3, characterized in that it comprises the following steps:
(1) mixing Co (NO) 3 ) 2 ·6H 2 Adding O, organic ligand 1, 2-bis (4-pyridine) ethylene and organic ligand tetrafluoro isophthalic acid into an organic solution, and fully dissolving by ultrasonic oscillation and magnetic stirring; transferring the mixed solution obtained by dissolving into a glass reaction bottle with a screw cap or a reaction kettle with a polytetrafluoroethylene lining, and heating for 24-48 h at 60-80 ℃ to obtain an orange homogeneous phase crystal material;
(2) filtering the obtained homogeneous phase crystal material, washing unreacted impurities by using N, N-dimethylformamide and methanol, and then placing the material in the 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 at the temperature of 70-120 ℃, and performing activation treatment for 24-48 h to obtain the novel porous coordination polymer material.
5. The process according to claim 4, wherein the organic ligands 1, 2-bis (4-pyridine) ethylene, organic ligands tetrafluoroisophthalic acid and Co (NO) in the step (1) 3 ) 2 ·6H 2 The molar ratio of O is 1: 0.1-10: 0.1 to 10.
6. The method according to claim 4, wherein the organic solvent in the step (1) is composed of N, N-dimethylformamide and methanol, and the volume ratio of the N, N-dimethylformamide to the methanol is 1: 0.1 to 10.
7. The method according to claim 4, wherein the time of the exchange treatment in the step (2) is 3 to 5 days, and the methanol is changed 2 to 3 times per day.
8. The method according to claim 4, wherein the filtration in step (3) is performed by using a glass sand core filtration device and an organic phase microporous membrane with a pore size of 0.2-0.5 μm.
9. Use of a porous coordination polymer according to any of claims 1 to 3, 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 The heterogeneous photocatalyst material of (1).
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Inventor after: Li Fengting

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