CN112724416B - Bio-based hydrogen bond organic framework material and preparation method and application thereof - Google Patents

Bio-based hydrogen bond organic framework material and preparation method and application thereof Download PDF

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CN112724416B
CN112724416B CN202011492960.6A CN202011492960A CN112724416B CN 112724416 B CN112724416 B CN 112724416B CN 202011492960 A CN202011492960 A CN 202011492960A CN 112724416 B CN112724416 B CN 112724416B
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boc
bpy
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butyloxycarbonyl
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CN112724416A (en
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于宝秋
王海龙
姜建壮
李连杰
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University of Science and Technology Beijing USTB
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Abstract

The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a preparation method of a high-performance organic photoelectric materialAnd a bio-based hydrogen bond organic framework material, a preparation method and application thereof. The bio-based hydrogen bond organic framework material is HOF-25-Re, and the HOF-25-Re is obtained by modifying metal Re in the prepared HOF-25. The bio-based hydrogen bond organic framework material is applied to heterogeneous photocatalysis CO2In the reduction, this is for the first time the application of the HOF material. The invention adopts guanine (intermediate Boc6G2bpy) as synthon, 5,5 '-diynyl-2, 2' -bipyridine as a building block, a novel rigid HOF was synthesized: HOF-25.

Description

Bio-based hydrogen bond organic framework material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a bio-based hydrogen bond organic framework material and a preparation method and application thereof.
Background
Reducing and fixing carbon dioxide emissions is a promising approach to address the growing energy crisis and global warming, which can export sustainable carbon fuels/chemicals while mitigating anthropogenic carbon dioxide emissions. In this regard, artificial photosynthesis using semiconductors, biological enzymes, and metal complexes facilitates the use of renewable solar energy to promote the circulation of carbon dioxide to fuel under mild conditions. Due to photocatalysis of CO2The conversion and hydrogen evolution reactions have thermodynamically similar redox potentials, and the inevitable competition between the two results in product mixing. Among various photocatalysts, molecular metal complexes show outstanding advantages in terms of molecular tailorability, mechanism research, product selectivity, price and the like. The molecular catalyst is combined with porous materials such as metal-organic frameworks (MOFs), Covalent Organic Frameworks (COFs), molecular sieves (Zeolite) and the like, so that the homogeneous catalyst has heterogeneity, is easy for product separation and catalytic polymerization, and obviously prolongs the service life of the catalyst. On the other hand, this heterogenization strategy achieved CO with excellent product selectivity2Continuous enrichment, diffusion and reduction.
Hydrogen-bonded organic frameworks (HOFs) are similar to MOFs and COFs in terms of bottom-up synthesis and porous periodic structures. HOFs are crystalline porous polymers, and are mainly formed by self-assembly of small organic molecular building units consisting of light elements (C, H, O, N, B and the like) through hydrogen bonds, pi-pi accumulation and van der Waals interaction. The composite material has the advantages of high specific surface area, porosity, low density, adjustable structure and the like, and has the advantages of two novel porous crystal materials of MOFs and COFs. In addition, because of the reversibility and flexibility of hydrogen bonding, HOFs exhibit high crystallinity, solution processability, and ease of repair and purification, and these unique advantages have led to their wide use in gas storage and separation, molecular recognition, electrical and optical materials, chemical sensing, catalysis, and biomedicine. However, the application of HOFs in the energy field is approaching the blank.
Disclosure of Invention
In order to achieve the purpose, the invention provides a bio-based hydrogen bond organic framework material and a preparation method and application thereof, and the bio-based hydrogen bond organic framework material is applied to heterogeneous photocatalysis CO2In the reduction, this is for the first time the application of the HOF material.
The invention is realized by the following technical scheme:
a bio-based hydrogen bond organic framework material is HOF-25-Re, wherein the HOF-25-Re is obtained by modifying metal Re in prepared HOF-25; the structural formula of the HOF-25-Re is as follows:
Figure BDA0002841233850000021
under visible light irradiation, [ Ru (bpy) ]in acetonitrile3]Cl2In the presence of a photosensitizer, the HOF-25-Re shows good heterogeneous catalysis performance on the carbon dioxide photoreduction reaction, and the yield is as high as 1448 mu mol g-1·h-1The selectivity is as high as 93 percent. Under the same photocatalytic conditions, the HOF-25-Re had an experimental TON of 50, which was a homogeneous control Re (bpy) (CO)3About 8 times Cl with [ Ru (bpy) ]3]Cl2To Re (bpy) (CO)3Compared with the only electron transfer of Cl, the HOF-25-Re has excellent photocatalytic performance (mainly electron transfer and energy transfer); warp beamThe photocatalysis performance of the HOF-25-Re after recrystallization and post-modification treatment is recovered; these effects highlight the advantages of HOFs in sustainable heterogenization of molecular catalysts.
Further, the intermediate product HOF-25 has a structural formula:
Figure BDA0002841233850000022
the invention also aims to provide a preparation method of the bio-based hydrogen bond organic framework material, which is used for preparing the HOF-25-Re material; the preparation method comprises the steps of preparing 5,5 '-dialkynyl-2, 2' -bipyridine and N2、N2、O6-tris (tert-butyloxycarbonyl) -N9-octyl-8-bromoguanosine, DMF, Et3N、Pd(PPh3)4And CuI as raw materials to prepare an intermediate product Boc6G2bpy; removing the intermediate Boc6G2A tert-butyloxycarbonyl (Boc) group in bpy to give intermediate HOF-25; finally HOF-25 and Re (CO)5And Cl is used as a raw material to prepare the HOF-25-Re.
Further, the preparation method specifically comprises the following steps:
s1 Synthesis of intermediate Boc6G2bpy: 5,5 '-dialkynyl-2, 2' -bipyridine and N2，N2，O6-tris (tert-butyloxycarbonyl) -N9Octyl-8-bromoguanosine, DMF and Et3Preparing degassed suspension with N, and adding Pd (PPh) respectively3)4And CuI; stirring the obtained mixture at constant temperature under the atmosphere of inert gas to obtain a reaction mixed solution; removing the organic phase from the reaction mixture under reduced pressure and eluting to obtain the intermediate Boc6G2bpy；
S2, synthesizing intermediate HOF-25: boc of the intermediate product at room temperature6G2bpy was dissolved in a mixture of dichloromethane and trifluoroacetic acid and allowed to stand for at least 55h to remove Boc6G2A tert-butyloxycarbonyl (Boc) group in bpy; then placed in a container containing MeOH in a closed chamber; finally, alcohol extraction, filtration and washing are carried out, and the HOF-25 is finally obtained;
s3, synthesizing HOF-25-Re material: the intermediate product HOF-25, Re (CO)5Mixing Cl, toluene and methanol to obtain a mixture; stirring the mixture under the conditions of constant temperature and inert gas atmosphere; and then filtering, washing and vacuum drying under reduced pressure to finally obtain the HOF-25-Re material.
Further, the elution in step S1 is performed with CHCl3the/EtOAc (300/15, 300/30, 300/40 to 300/50) eluent was passed successively through a silica gel column.
Further, the intermediate Boc in step S16G2bpy was a yellow viscous oil that slowly solidified to a solid in 16.1% yield (110.0 mg).
Further, the intermediate Boc 1 was prepared6G2The chemical reaction equation for bpy is:
Figure BDA0002841233850000031
further, DMF is used as a solvent in step S1 (hereinafter, the amount of DMF is used as a standard); et in step S13N is also a solvent, and the dosage is one half of DMF.
Further, in step S1, the 5,5 '-diynyl-2, 2' -bipyridine is used in an amount of 14.0 to 18.0mg/ml (DMF).
Further, said N in step S12，N2，O6-tris (tert-butyloxycarbonyl) -N9The amount of octyl-8-bromoguanosine is 225.0-310.0mg/ml (DMF).
Further, Pd (PPh) in step S13)4The amount is 1.5-2.5mg/ml (DMF).
Further, in step S1, the amount of CuI is 0.5-2.0mg/ml (DMF).
Further, the constant temperature in S1 is 45-65 ℃; the inert gas is nitrogen, argon or helium; the stirring time is at least 40.0 h.
Further, the dichloromethane is used as a solvent in step S2 (the amount of S2 is based on the amount of dichloromethane).
Further, the amount of trifluoroacetic acid (TFA) used in step S2 is between one-fourth and one-half of the volume of dichloromethane.
Further, the intermediate Boc in step S26G2The bpy dosage is 7.5-25mg/ml (CH)2Cl2)。
Further, in step S2, the alcohol extraction specifically includes: HOF-25 was prepared using slow diffusion of methanol in solution and slow evaporation of the solvent.
Further, the detergent for washing in step S2 is one or more of excess dichloromethane, chloroform, methanol, and ethanol.
Further, Boc was removed in S26G2The chemical reaction formula for the tertiary butyloxycarbonyl (Boc) group of bpy is:
Figure BDA0002841233850000041
further, toluene is used as a solvent in step S3 (the amount of toluene is used as a standard);
in step S3, the amount of methanol is between one fifth and one tenth of toluene.
Further, the intermediate HOF-25 in step S3 is used in an amount of 2.0-3.0mg/ml (C)7H8)。
Further, the Re (CO) in step S35The Cl dosage is 1.5-2.0mg/ml (C)7H8)。
Further, the constant temperature in S3 is 45-65 ℃, and the inert gas is one or more of nitrogen, argon and helium.
Further, the stirring time in S3 is at least 36.0 h.
Further, washing in S3 with toluene/methanol (v: v ═ 10:1, 10.0 × 3ml) gave an orange solid; drying at room temperature under reduced pressure for at least 5.0 h.
Further, the intermediate HOF-25 and Re (CO) in S35The reaction formula of Cl is:
Figure BDA0002841233850000051
further, the HOF-25-Re material obtained by the preparation method has a rare earth content of 1.1 wt% determined by an ICP-MS method.
The invention also aims to provide application of the bio-based hydrogen bond organic framework material, in particular to application of the HOF-25-Re material in photocatalysis of CO2The use of (1).
The invention has the following beneficial technical effects:
1) the invention adopts guanine (intermediate Boc6G2bpy) as synthon, 5,5 '-diynyl-2, 2' -bipyridine as a building block, a novel rigid HOF was synthesized: HOF-25.
2) The invention uses Re (CO)5The first HOF-based heterogeneous catalyst for photocatalytic carbon dioxide reduction was prepared by post-modification of 5,5 '-diynyl-2, 2' -bipyridine with Cl: HOF-25-Re.
Drawings
FIG. 1 shows the powder diffraction spectrum and the crystal face assignment of the intermediate HOF-25 in the example of the present invention.
FIG. 2 is a carbon dioxide adsorption and desorption curve of intermediate products HOF-25 and HOF-25-Re materials at a temperature of 196K in the embodiment of the invention.
FIG. 3 shows the intermediate HOF-25, HOF-25-Re material and monomer control Re (bpy) (CO) in an example of the present invention3Ir spectrum of Cl.
Fig. 4 is a powder diffraction pattern of intermediate product HOF-25 in the example of the present invention after soaking in an aqueous solution of pH 7-11 for one week.
FIG. 5 is a powder diffraction pattern of the intermediate HOF-25 soaked in different organic solvents for one week in the examples of the present invention.
FIG. 6 is a graph of the photocatalytic carbon dioxide recycling rate for the HOF-25-Re material in an example of the present invention.
FIG. 7 shows an embodiment of the invention in which HOF-25-Re material and Re (bpy) (CO)3TON (number of catalytic cycles) versus Cl.
FIG. 8 is a photo-catalytic carbon dioxide reduction graph of HOF-25-Re material under different conditions in an example of the present invention.
FIG. 9 shows an intermediate Boc in an example of the present invention6G2Nuclear magnetic resonance hydrogen spectrum of bpy.
FIG. 10 is an intermediate Boc in an example of the invention6G2Nuclear magnetic resonance carbon spectrum of bpy.
FIG. 11 is a NMR spectrum of intermediate HOF-25 in example of the present invention.
FIG. 12 is a nuclear magnetic resonance carbon spectrum of intermediate HOF-25 in the example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
In the embodiment, a biobased hydrogen bond organic framework material is provided, the biobased hydrogen bond organic framework material is HOF-25-Re, and the HOF-25-Re is obtained by modifying metal Re in the prepared HOF-25; the structural formula of the HOF-25-Re is as follows:
Figure BDA0002841233850000061
in acetonitrile [ Ru (bp) under irradiation with visible lighty)3]Cl2In the presence of a photosensitizer, the HOF-25-Re shows good heterogeneous catalysis performance on the carbon dioxide photoreduction reaction, and the yield is as high as 1448 mu mol g-1·h-1The selectivity is as high as 93 percent. Under the same photocatalytic conditions, the HOF-25-Re had an experimental TON of 50, which was a homogeneous control Re (bpy) (CO)3About 8 times Cl with [ Ru (bpy) ]3]Cl2To Re (bpy) (CO)3Compared with the only electron transfer of Cl, the HOF-25-Re has excellent photocatalytic performance (mainly electron transfer and energy transfer); the photocatalysis performance of the HOF-25-Re after recrystallization and post-modification treatment is recovered; these effects highlight the advantages of HOFs in sustainable heterogenization of molecular catalysts.
In this example, the intermediate HOF-25 has the formula:
Figure BDA0002841233850000071
in the embodiment, the preparation method of the bio-based hydrogen bond organic framework material is also provided, and is used for preparing the HOF-25-Re material; the preparation method comprises the steps of preparing 5,5 '-dialkynyl-2, 2' -bipyridine and N2、N2、O6-tris (tert-butyloxycarbonyl) -N9-octyl-8-bromoguanosine, DMF, Et3N、Pd(PPh3)4And CuI as raw materials to prepare an intermediate product Boc6G2bpy; removing the intermediate Boc6G2A tert-butyloxycarbonyl (Boc) group in bpy to give intermediate HOF-25; finally HOF-25 and Re (CO)5And Cl is used as a raw material to prepare the HOF-25-Re.
In this embodiment, the preparation method specifically includes the following steps:
s1 Synthesis of intermediate Boc6G2bpy: 5,5 '-dialkynyl-2, 2' -bipyridine and N2，N2，O6-tris (tert-butyloxycarbonyl) -N9Octyl-8-bromoguanosine, DMF and Et3Preparing degassed suspension with N, and adding Pd (PPh) respectively3)4And CuI; stirring the obtained mixture at constant temperature under the atmosphere of inert gas to obtain a reaction mixed solution; removing the organic phase from the reaction mixture under reduced pressure and eluting to obtain the intermediate Boc6G2bpy；
S2, synthesizing intermediate HOF-25: boc of the intermediate product at room temperature6G2bpy was dissolved in a mixture of dichloromethane and trifluoroacetic acid and allowed to stand for at least 55h to remove Boc6G2A tert-butyloxycarbonyl (Boc) group in bpy; placing in a closed chamber containing MeOH; finally, alcohol extraction, filtration and washing are carried out, and the HOF-25 is finally obtained;
s3, synthesizing HOF-25-Re material: the intermediate product HOF-25, Re (CO)5Mixing Cl, toluene and methanol to obtain a mixture; stirring the mixture under the conditions of constant temperature and inert gas atmosphere; and then filtering, washing and vacuum drying under reduced pressure to finally obtain the HOF-25-Re material.
In the present embodiment, the elution in step S1 is performed with CHCl3the/EtOAc (300/15, 300/30, 300/40 to 300/50) eluent was passed successively through a silica gel column.
In this example, the intermediate Boc in step S16G2bpy was a yellow viscous oil that slowly solidified to a solid in 16.1% yield (110.0 mg).
In this example, the intermediate Boc 1 was prepared6G2The chemical reaction equation for bpy is:
Figure BDA0002841233850000081
in this example, DMF is used as the solvent in step S1 (the amount of DMF is used as the standard); et in step S13N is also a solvent, and the dosage is one half of DMF.
In this example, the 5,5 '-diynyl-2, 2' -bipyridine used in step S1 was 17.67mg/ml (DMF).
In another embodiment, the 5,5 '-diynyl-2, 2' -bipyridine in step S1 is present in an amount of 18.0mg/ml (DMF).
In other embodiments, the 5,5 '-diynyl-2, 2' -bipyridine in step S1 is used in an amount of 14.0mg/ml (DMF), 15.0mg/ml (DMF), 16.0mg/ml (DMF), or 17.0mg/ml (DMF), respectively.
In this embodiment, N is set in step S12，N2，O6-tris (tert-butyloxycarbonyl) -N9The amount of octyl-8-bromoguanosine was 275.0mg/ml (DMF).
In another embodiment, said N in step S12，N2，O6-tris (tert-butyloxycarbonyl) -N9Octyl-8-bromoguanosine was used in an amount of 225.0mg/ml (DMF).
In other embodiments, said N in step S12，N2，O6-tris (tert-butyloxycarbonyl) -N9Octyl-8-bromoguanosine at 230.0mg/ml (DMF), 235.0mg/ml (DMF), 245.0mg/ml (DMF), 255.0mg/ml (DMF), 265.0mg/ml (DMF), 275.0mg/ml (DMF), 285.0mg/ml (DMF), 295.0mg/ml (DMF), 300.0mg/ml (DMF), 305.0mg/ml (DMF), or 310.0mg/ml (DMF).
In the present embodiment, Pd (PPh) in step S13)4The amount used was 2.0mg/ml (DMF).
In another embodiment, the Pd (PPh) in step S13)4The amount used was 1.5mg/ml (DMF).
In other embodiments, the Pd (PPh) in step S13)4The amount used was 2.5mg/ml (DMF).
In this example, the amount of CuI used in step S1 is 0.5mg/ml (DMF).
In another embodiment, the amount of CuI used in step S1 is 2.0mg/ml (DMF).
In other embodiments, the amount of CuI used in step S1 is 1.0mg/ml (DMF) or 1.5mg/ml (DMF).
In the embodiment, the constant temperature in the S1 is 50 ℃; the inert gas is nitrogen, argon or helium; the stirring time is at least 40.0 h.
In this example, the dichloromethane in step S2 is used as the solvent (the amounts of other raw materials in S2 are all based on the amount of dichloromethane).
In this embodiment, the amount of trifluoroacetic acid (TFA) used in step S2 is between one-fourth and one-half of the volume of dichloromethane.
In this example, the intermediate Boc in step S26G2The dosage of bpy is 7.5mg/ml (CH)2Cl2)。
In another embodiment, the intermediate Boc product of step S26G2The dosage of bpy is 25mg/ml (CH)2Cl2)。
In other embodiments, the intermediate Boc product of step S26G2The dosage of bpy is 10.0mg/ml (CH)2Cl2)、11.0mg/ml(CH2Cl2)、12.0mg/ml(CH2Cl2)、13.0mg/ml(CH2Cl2)、14.0mg/ml(CH2Cl2)、15.0mg/ml(CH2Cl2)、16.0mg/ml(CH2Cl2)、17.0mg/ml(CH2Cl2)、18.0mg/ml(CH2Cl2)、19.0mg/ml(CH2Cl2)、20.0mg/ml(CH2Cl2)、21.0mg/ml(CH2Cl2)、22.0mg/ml(CH2Cl2)、23.0mg/ml(CH2Cl2)、24.0mg/ml(CH2Cl2) Or 25.0mg/ml (CH)2Cl2)。
In this embodiment, the alcohol extraction in step S2 specifically includes: HOF-25 was prepared using slow diffusion of methanol in solution and slow evaporation of the solvent.
In this embodiment, the detergent used in step S2 is one or more of excess dichloromethane, chloroform, methanol and ethanol.
In this example, Boc was removed in S26G2The chemical reaction formula for the tertiary butyloxycarbonyl (Boc) group of bpy is:
Figure BDA0002841233850000091
in this embodiment, the toluene is used as a solvent in step S3 (the amount of toluene is used as a standard);
in step S3, the amount of methanol is between one fifth and one tenth of toluene.
In this example, the amount of the intermediate HOF-25 used in step S3 was 2.5mg/ml (C)7H8)。
In another embodiment, the intermediate HOF-25 is used in an amount of 2.0mg/ml (C) in step S37H8)。
In other embodiments, the intermediate HOF-25 is used in an amount of 3.0mg/ml (C) in step S37H8). In this embodiment, Re (CO) in step S35The amount of Cl used was 1.75mg/ml (C)7H8)。
In another embodiment, the Re (CO) of step S35The amount of Cl used was 1.5mg/ml (C)7H8)。
In other embodiments, the Re (CO) of step S35The amount of Cl used was 2.0mg/ml (C)7H8). In this embodiment, the constant temperature in S3 is 50 ℃, and the inert gas is one or more of nitrogen, argon, and helium.
In this example, the stirring time in S3 is at least 36.0 h.
In this example, the wash in S3 was with toluene/methanol (v: v ═ 10:1, 10.0 × 3ml) to give an orange solid; drying at room temperature under reduced pressure for at least 5.0 h.
In this example, intermediate HOF-25 and Re (CO) described in S35The reaction formula of Cl is:
Figure BDA0002841233850000101
referring to FIG. 9, FIG. 10, FIG. 11 and FIG. 12, in this example, Boc to be synthesized6G2Nuclear magnetic analyses were performed in bpy and HOF-25 to show the structure and purity of the synthesized molecules.
In this example, the HOF-25-Re material obtained by the preparation method had a rare earth content of 1.1 wt% as measured by an ICP-MS method.
In this embodiment, the method for determining the structure of intermediate product HOF-25 is as follows:
(1) powder X-ray diffraction (PXRD) data were collected at room temperature using a PANalytical Empyrean series 3 diffractometer with instrument parameters: the method adopts a graphite monochromized Cu target as an X-ray light source, and the test voltage is as follows: 50KV, test current: 40mA, the test step size is: 0.01313 deg. 2 theta. The periodicity of the HOF-25 structure was studied by powder X-ray diffraction (PXRD) analysis. The strong peak appearing at 3.47 ° and the relatively weak peaks at 4.72 °, 6.93 °, 10.38 °, 12.75 °, 13.83 ° and 25.80 ° in the PXRD pattern are assigned to the (100), (110), (200), (300), (320), (400) and (001) crystal planes, respectively. (100) The strong diffraction intensity of the (200) and (300) crystal planes and the weak diffraction of the crystal planes imply long-range order of HOF-25 in the ab plane. An AA stacking structure model of HOF-25 with space group P4/m is established by using Materials Studio software package, and the simulated PXRD pattern is basically consistent with the experimental synthesis result. The slight difference in the 15-25 ° range is probably due to the inclusion of solvent guest in the HOFs pores. As shown in fig. 1.
(2) Carbon dioxide adsorption and desorption isotherms for HOF-25 and HOF-25-Re were measured at 196K using a Micromeritics ASAP 2020PLUS HD88 and the samples were degassed at room temperature for 10.0 hours before measurement. The BET areas are respectively: 111m2G and 96m2(ii) in terms of/g. The HOF-25 and HOF-25-Re were subjected to gas adsorption and specific surface area test, showing that they had a permanent pore structure, as shown in FIG. 2.
(3) HOF-25, HOF-25-Re and monomer controls were tested on a Bruker-tensor37 spectrometer using a KBr pellet: re (bpy) (CO)3IR spectrum of Cl with resolution of 1cm-1. As shown in fig. 3.
(4) Soaking HOF-25 in an aqueous solution with pH of 7-11 and an organic solvent such as toluene, acetonitrile, methanol, tetrahydrofuran and the like for one week, and filtering to measure the PXRD (determining the periodic structure and the structural stability of the HOF-25 and the HOF-25-Re) to characterize the structural stability; as shown in fig. 4 and 5.
In this embodiment, there is also provided aThe application of a bio-based hydrogen bond organic framework material, in particular to the application of the HOF-25-Re material in photocatalysis of CO2The use of (1).
In this example, the HOF-25-Re material was used to photocatalyze CO2The specific contents of the application are as follows:
the HOF-25-Re material was dispersed in CH as a catalyst (5.0mg)3CN (18.0mL), followed by [ Ru (bpy)3]Cl2·6H2O (9.5mg), 2' -bipyridine (15.0mg), and triisopropanolamine (TIPA, 2.0mL) and sonicated for 5.0 min;
in degassing and CO charging2After the three times, the photocatalytic system is vigorously stirred and kept at room temperature under the irradiation of a 300w xenon lamp and an ultraviolet cut-off filter (lambda is more than or equal to 420 nm);
every 0.5 hours, the obtained gas product (0.5mL) was sampled with a gas-tight syringe and analyzed using a gas chromatograph (GC 7920);
CO and H measurements with Thermal Conductivity Detector (TCD) and Flame Ionization Detector (FID), respectively2. And (4) identifying the experimental components and the gas production by using standard gas.
(2) The control experiment was performed in the absence of light, photosensitizer, catalyst, sacrificial agent and carbon dioxide. In the recovery experiment, HOF-25-Re was centrifuged from the reaction mixture, washed 3 times with acetonitrile (20.0ml) and then reused in the above-mentioned photocatalytic system. Relatively homogeneous Re (bpy) (CO)3Cl catalyst [ Ru (bpy)3]Cl2·6H2O (9.5mg) was added to the photocatalytic mixture after 2.0h of photocatalytic reaction for cyclic experiments. As shown in fig. 6, 7, 8.

Claims (10)

1. A bio-based hydrogen bond organic framework material is characterized in that the bio-based hydrogen bond organic framework material is HOF-25-Re; the structural formula of the HOF-25-Re is as follows:
Figure FDA0003462184180000011
2. the method for preparing bio-based hydrogen bonding organic framework material according to claim 1, wherein the preparation method comprises the steps of preparing 5,5 '-dialkynyl-2, 2' -bipyridine and N2,N2,O6-tris (tert-butyloxycarbonyl) -N9-octyl-8-bromoguanosine, DMF, Et3N、Pd(PPh3)4And CuI as raw materials to prepare an intermediate product Boc6G2bpy; removing the intermediate Boc6G2A tert-butyloxycarbonyl (Boc) group in bpy to give intermediate HOF-25; finally HOF-25 and Re (CO)5Preparing the HOF-25-Re by taking Cl as a raw material;
said N is2,N2,O6-tris (tert-butyloxycarbonyl) -N9The structural formula of the (E) -octyl-8-bromoguanosine is as follows:
Figure FDA0003462184180000012
3. the preparation method according to claim 2, characterized in that the preparation method comprises the following steps:
s1 Synthesis of intermediate Boc6G2bpy: 5,5 '-dialkynyl-2, 2' -bipyridine and N2,N2,O6-tris (tert-butyloxycarbonyl) -N9Octyl-8-bromoguanosine, DMF and Et3Preparing degassed suspension with N, and adding Pd (PPh) respectively3)4And CuI; stirring the obtained mixture at constant temperature under the atmosphere of inert gas to obtain a reaction mixed solution; removing the organic phase from the reaction mixture under reduced pressure and eluting to obtain the intermediate Boc6G2bpy；
S2, synthesizing intermediate HOF-25: boc of the intermediate product at room temperature6G2bpy was dissolved in a mixture of dichloromethane and trifluoroacetic acid and allowed to stand for at least 55h to remove Boc6G2A tert-butyloxycarbonyl (Boc) group in bpy; placing in a closed chamber containing MeOH; finally alcohol extraction is carried out,Filtering and washing to finally obtain the HOF-25;
s3, synthesizing HOF-25-Re material: the intermediate product HOF-25, Re (CO)5Mixing Cl, toluene and methanol to obtain a mixture; stirring the mixture under the conditions of constant temperature and inert gas atmosphere; and then filtering, washing and vacuum drying under reduced pressure to finally obtain the HOF-25-Re material.
4. The method of claim 3, wherein the intermediate Boc 1 is prepared in S16G2The chemical reaction equation for bpy is:
Figure FDA0003462184180000021
5. the method according to claim 3, wherein the 5,5 '-diynyl-2, 2' -bipyridine is used in an amount of 14.0 to 18.0mg/(ml DMF) in step S1;
said N is2，N2，O6-tris (tert-butyloxycarbonyl) -N9The dosage of the-octyl-8-bromoguanosine is 225.0-310.0mg/(ml DMF);
the Pd (PPh)3)4The dosage is 1.5-2.5mg/(ml DMF);
the dosage of the CuI is 0.5-2.0mg/(ml DMF).
6. The method of claim 3, wherein the intermediate Boc 2 is used in step S26G2The dosage of bpy is 7.5-25 mg/(mlCH)2Cl2)。
7. The method of claim 3, wherein the Boc is removed in step S26G2The chemical reaction formula for the tertiary butyloxycarbonyl (Boc) group of bpy is:
Figure FDA0003462184180000022
8. the method according to claim 3, wherein the intermediate HOF-25 is used in an amount of 2.0 to 3.0mg/(ml of toluene) in step S3;
the Re (CO)5The Cl dosage is 1.5-2.0mg/(ml toluene).
9. The method of claim 3, wherein the intermediate HOF-25 and Re (CO) of step S35The reaction formula of Cl is:
Figure FDA0003462184180000031
10. use of the biobased hydrogen bonding organic framework material as claimed in claim 1, wherein the HOF-25-Re material is used for photocatalysis of CO2In (1).
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