CN117209790A - Cadmium coordination polymer capable of fully absorbing visible light and preparation method and application thereof - Google Patents
Cadmium coordination polymer capable of fully absorbing visible light and preparation method and application thereof Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 49
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 49
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 26
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- BVQAWSJMUYMNQN-UHFFFAOYSA-N dipyridophenazine Chemical compound C1=CC=C2C3=NC4=CC=CC=C4N=C3C3=CC=CN=C3C2=N1 BVQAWSJMUYMNQN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 26
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- NMQPIBPZSLMCFI-UHFFFAOYSA-N 2-(4-methylphenyl)acetamide Chemical compound CC1=CC=C(CC(N)=O)C=C1 NMQPIBPZSLMCFI-UHFFFAOYSA-N 0.000 claims abstract description 9
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002950 deficient Effects 0.000 claims abstract description 6
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims abstract description 5
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000002399 angioplasty Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000031700 light absorption Effects 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011358 absorbing material Substances 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000013354 porous framework Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000032900 absorption of visible light Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 238000005580 one pot reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000488913 Olax Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to the field of functional crystal materials, in particular to a cadmium coordination polymer capable of fully absorbing visible light, and a preparation method and application thereof. The chemical formula is { [ Cd ] 2 (dppz) 2 (PTA) 2 (H 2 O) 2 ](TTF) 0.5 } n Designated HGCP-14, wherein the primary ligand is electron-deficient bipyrido [3,2-a:2',3' -c]Phenazine (dppz), the ancillary ligand is terephthalic acid (H) 2 PTA), the solvent is a mixed solution of N, N-Dimethylformamide (DMF), methanol, water and fluoroboric acid, and the guest molecule is tetrathiafulvalene (TTF). The coordination polymer has higher thermal stability, and the synthesis of the cadmium coordination polymer material with the functions of full absorption of visible light and near infrared short wave absorption is realized for the first time through the action of entrapment of guest molecule TTF (TTF) as a first donor-acceptor.
Description
Technical Field
The invention relates to the field of functional crystal materials, in particular to a cadmium coordination polymer capable of fully absorbing visible light, and a preparation method and application thereof.
Background
A light absorbing material is a special material that has the ability to absorb light, the basic principle being that it is able to absorb light of a specific wavelength by its special structure and chemical composition. This absorption process may result in the conversion of light energy into other forms of energy, such as thermal energy, electrical energy, and the like. Therefore, light absorbing materials find important applications in many fields, such as solar panels, optical devices, infrared imaging, and energy storage.
In recent years, coordination Polymers (CPs) have received attention as a novel inorganic-organic hybrid functional material formed by combining metal ions and organic ligands through coordination bonds. The material has the characteristics of unique component diversity, structural designability, adjustable porosity and the like, and has excellent performances in the fields of gas adsorption and separation, catalysis, luminescence, drug slow release, energy storage and the like. At present, research on doping coordination polymer materials for solar cells is carried out, but research on the coordination polymer as a light absorption material is rarely reported, and the material generally only absorbs part of visible light or ultraviolet light.
The invention utilizes the coordination polymer containing electron-deficient ligand as an acceptor host framework, introduces electron-rich donor guest molecule tetrathiafulvalene into the pores of the coordination polymer, and realizes the preparation of the cadmium coordination polymer with visible light total absorption and near infrared short wave absorption for the first time. The cadmium coordination polymer prepared by the invention is taken as a novel light absorption material, is expected to be applied to the fields of solar cells, up-conversion luminescent materials, optical and energy storage equipment and the like, and has important reference value for realizing sustainable development and solving energy problems.
Disclosure of Invention
Aiming at the technical analysis and problems, the invention provides a cadmium coordination polymer capable of absorbing all visible light and near infrared short waves, a preparation method and application thereof, wherein the coordination polymer has a wide absorption spectrum, can well absorb light waves within a range of 350-1000nm, has a forbidden band width of 1.453eV, can be used as a potential light absorption material, and has good application prospect in the fields of solar cells, up-conversion luminescent materials, optics and energy storage equipment.
The invention is realized by adopting the following technical scheme:
a cadmium coordination polymer capable of absorbing all visible light and near infrared short waves has a chemical formula of { [ Cd ] 2 (dppz) 2 (PTA) 2 (H 2 O) 2 ](TTF) 0.5 } n Designated HGCP-14, wherein the primary ligand is electron-deficient bipyrido [3,2-a:2',3' -c]Phenazine (dppz), the ancillary ligand is terephthalic acid (H) 2 PTA), the solvent is a mixed solution of N, N-Dimethylformamide (DMF), methanol, water and fluoroboric acid, and the guest molecule is tetrathiafulvalene (TTF).
Based on the scheme, further, the cadmium coordination polymer HGCP-14 is crystallized in a monoclinic systemC2/cSpace group, unit cell parameters are:a= 29.817(5) Å，b= 9.5758(13)Å，c= 20.821(3)Å；α=90°，β= 104.301(5)°，γ= 90°。
based on the scheme, the cadmium coordination polymer HGCP-14 is further characterized in that: the frame is internally provided with a one-dimensional chain structure formed by PTA ligand and cadmium ion coordination, adjacent chains are piled together through intermolecular force, dppz ligand is chelate end group coordination, a three-dimensional supermolecule porous frame structure is finally formed, the pore canal wall is an electron-deficient phenazine unit, and electron-rich guest TTFs are orderly arranged in the pore canal;
in the asymmetric structural unit of HGCP-14, there is a crystal independent Cd (II), a dppz ligand, a PTA 2- A ligand, a coordinated water molecule and half a TTF molecule. Cd (II) adopts seven coordination, and is respectively matched with two PTAs from different PTAs 2- Four carboxyl oxygen atoms of the ligand, two pyridine nitrogen atoms of one dppz ligand and 1 water molecule coordinate to form a pentagonal bipyramid geometric configuration; adjacent Cd (II) passes through PTA 2– The ligand carboxyl oxygen atoms are coordinately connected to form a one-dimensional chain structure extending along the direction y of the c axis, and pyridine nitrogen atoms on dppz ligands are distributed on two sides of the one-dimensional chain in an end group chelating coordination mode and are distributed in an antiparallel mode;
the chains are overlapped and arranged along an a axis and a b axis by ABAB to form a three-dimensional supermolecule framework structure, a one-dimensional rectangular channel is formed along the b axis, and free TTF guest molecules are arranged in the channel; TTF acts as a donor and forms a donor-acceptor effect with the acceptor dppz containing the phenazine deficiency electron unit on the pore channel wall.
Based on the scheme, the cadmium coordination polymer further has an absorption effect on visible light and near-infrared short wave light waves in the range of 350-1000nm, and a lower forbidden bandwidth value of 1.453eV is obtained through absorption spectrum fitting.
The invention also provides a preparation method of the cadmium coordination polymer capable of absorbing all visible light and near infrared short waves, namely, a one-pot method is adopted, and metal salt, ligand and guest molecules are simultaneously added into an organic solvent for reaction by utilizing in-situ synthesis, so that the coordination polymer crystal material with the visible light full absorption and near infrared short wave absorption properties can be obtained.
The method specifically comprises the following steps:
1) The organic ligand dppz, H 2 PTA, cadmium nitrate and corresponding guest TTF molecules are added into a mixed solvent of DMF, methanol, water and fluoboric acid and are uniformly mixed;
2) Sealing the obtained mixed liquid, performing solvothermal reaction at 80-120 ℃ for 24-72 hours, and naturally cooling to room temperature to obtain black brown long strip crystals;
3) And washing the crystal with DMF and drying to obtain the coordination polymer HGCP-14 with light absorption performance.
Based on the scheme, further, the molar ratio of dppz, PTA, cadmium nitrate and the guest molecule is 1:1-2:1-3:0.5-1.
Based on the scheme, the volume ratio of DMF, methanol, water and fluoroboric acid is 10-20:10-20:0.5-1; the ratio of dppz to the amount of the mixed solvent was 0.05 mmol: 5-10 ml.
The invention also provides application of the cadmium coordination polymer as a light absorption material, wherein the cadmium coordination polymer can absorb visible light and near infrared short wave light waves within the range of 350-1000nm and has a lower forbidden bandwidth.
The beneficial technical effects of the invention are as follows: the coordination polymer has higher thermal stability, and through the action of inclusion of guest molecule TTF, the synthesis of the cadmium coordination polymer material with the functions of full absorption of visible light and near infrared short wave absorption is realized for the first time, and the synthesis technology has universality and solves the problem of small light absorption range of the material to a certain extent. The powder diffraction pattern obtained by experiment is basically identical with theoretical simulation, and the phase purity is higher. The material has the characteristics of large light absorption range and low forbidden bandwidth, is expected to be used as a light absorption material in the fields of solar batteries, up-conversion luminescent materials, optical and energy storage equipment and the like, and has good application prospect.
Description of the drawings:
FIG. 1 is a diagram of the coordination environment of HGCP-14 (a) and the coordination mode of terephthalic acid in its structure (b).
FIG. 2 is an overall block diagram of HGCP-14.
FIG. 3 is an X-ray powder diffraction pattern of HGCP-14.
FIG. 4 is a thermogravimetric analysis of HGCP-14.
FIG. 5 is a graph (b) showing the absorption spectrum (a), crystal color and band gap profile of HGCP-14.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
cd (NO) 3 ) 2 ·4H 2 O（24.6mg，0.1mmol）、dppz（14.1mg，0.05mmol）、H 2 PTA (8.3 mg,0.05 mmol) and TTF (10.2 mg,0.05 mmol) were placed in a 10mL vial and DMF (1.5 mL), methanol (1.5 mL), deionized water (1.5 mL), fluoroboric acid (0.15 mL) was added. And (3) carrying out ultrasonic treatment for 10 min after sealing until the solution is clear, and then placing the solution into a baking oven at the temperature of 90-100 ℃ for constant temperature heating for 24-36 h to obtain black brown long strip crystals.
Example 2:
cd (NO) 3 ) 2 ·4H 2 O（36.9mg，0.15mmol）、dppz（14.1mg，0.05mmol）、H 2 PTA (8.3 mg,0.05 mmol) and TTF (10.2 mg,0.05 mmol) were placed in a 10mL vial and DMF (2 mL), methanol (2 mL), deionized water (2 mL), fluoroboric acid (0.1 mL) was added. And (3) carrying out ultrasonic treatment for 10 min after sealing until the solution is clear, and then placing the solution into an oven at 80-90 ℃ for constant temperature heating for 36-48 h to obtain black brown long strip crystals.
Example 3:
cd (NO) 3 ) 2 ·4H 2 O（36.9mg，0.15mmol）、dppz（14.1mg，0.05mmol）、H 2 PTA (16.6 mg,0.1 mmol) and TTF (10.2 mg,0.05 mmol) were placed in a 10mL vial and DMF (2.5 mL), methanol (2.5 mL), deionized water (2.5 mL), fluoroboric acid (0.16 mL) was added. And (3) carrying out ultrasonic treatment for 10 min after sealing until the solution is clear, and then placing the solution into a baking oven at 105-120 ℃ for constant temperature heating for 24-30 h to obtain black brown long strip crystals.
Example 4:
cd (NO) 3 ) 2 ·4H 2 O（36.9mg，0.15mmol）、dppz（28.2mg，0.1mmol）、H 2 PTA (16.6 mg,0.1 mmol) and TTF (20.4 mg,0.1 mmol) were placed in a 10mL vial and DMF (3 mL), methanol (3 mL) was addedDeionized water (3 mL), fluoroboric acid (0.2 mL). And (3) carrying out ultrasonic treatment for 10 min after sealing until the solution is clear, and then placing the solution into an oven at 80-85 ℃ to heat at constant temperature for 54-72 h, thus obtaining black brown long-strip crystals.
Characterization of the coordination polymer produced:
(1) Crystal structure determination
Appropriate crystals were selected under a microscope, stuck to glass filaments, and diffraction data were collected using a bruker APEXII single crystal diffractometer at different temperatures (193K, 298K) and targets (copper palladium, molybdenum targets). The diffractometer was prepared by a method comprising the step of monochromating K with a graphite monochromatoraRays, data are acquired in a phi-omega manner. During data reduction, the SADABS procedure was used for empirical absorption and correction. And solving the structure by adopting a direct method, and optimizing based on the F2 full matrix least square method by utilizing a SHELXTL software package. To further refine the crystal data, the refinement was performed using olax 2 software. When finishing to the last round, anisotropic finishing is carried out on non-hydrogen atoms, and the position of the hydrogen atoms on the ligand is determined by a theoretical hydrogenation method. The crystallographic data are shown in table 1.
TABLE 1 Crystal data and Structure refinement parameters of coordination Polymer HGCP-14
(2) Characterization of phase purity by powder diffraction
To examine the phase purity and crystallinity of the samples, X-ray powder diffraction tests were performed on freshly synthesized samples in the 5-50 ° range.
The powder diffraction spectrum of the single crystal structure was converted using Mercury 1.4.2.
FIG. 3 is a powder diffraction pattern of the coordination polymer, showing that: the experimental diffraction peak is substantially coincident with the diffraction peak position compared to the simulated peak, which indicates that the coordination polymer has higher phase purity.
(3) Thermal stability
FIG. 4 is a thermogravimetric analysis of the coordination polymer showing: the decomposition temperature of the coordination framework of the material is about 335 ℃, which shows that the coordination polymer has good thermal stability.
(4) Study of light absorption Properties
The coordination polymer is applied to a solid light absorption material, and the synthesis method is characterized in that a one-pot method is adopted, and metal salt, ligand and guest molecules are simultaneously added into an organic solvent for reaction by utilizing in-situ synthesis, so that the coordination polymer crystal material with the properties of full absorption of visible light and near infrared short wave absorption can be obtained.
FIG. 5 shows a fitted graph of absorption spectrum and forbidden band width of the coordination polymer, wherein: the coordination polymer has an absorption effect on visible light and near-infrared short wave light waves within the range of 350-1000nm, and a lower forbidden bandwidth value of 1.453eV is obtained through absorption spectrum fitting, which proves the advantage that the coordination polymer generates wide-range light absorption performance through the donor-acceptor effect, is expected to be applied to the fields of solar cells, up-conversion luminescent materials, optical and energy storage devices and the like, and provides a new thought for the design and synthesis of novel light absorption materials.
Claims (7)
1. A visible light total absorption cadmium coordination polymer is characterized in that: the chemical formula is { [ Cd ] 2 (dppz) 2 (PTA) 2 (H 2 O) 2 ](TTF) 0.5 } n Designated HGCP-14, wherein the primary ligand is electron-deficient bipyrido [3,2-a:2',3' -c]Phenazine (dppz), the ancillary ligand is terephthalic acid (H) 2 PTA), wherein the solvent is a mixed solution of N, N-Dimethylformamide (DMF), methanol, water and fluoroboric acid, and the guest molecule is tetrathiafulvalene (TTF);
in the asymmetric structural unit of the crystal structure of HGCP-14, there is a crystallographic independent Cd (II), a dppz ligand, a PTA 2- A ligand, a coordinated water molecule and half of a TTF molecule;
an electron-rich object TTF is orderly arranged in a pore canal of a crystal framework of the cadmium coordination polymer HGCP-14, and the TTF is used as a donor and forms a donor-acceptor effect with an acceptor dppz containing a phenazine electron-deficient unit on the pore canal wall.
2. The visible light totally absorbing cadmium coordination polymer according to claim 1, wherein: the cadmium coordination polymer HGCP-14 is crystallized in a monoclinic systemC2/cSpace group, unit cell parameters are:a= 29.817(5) Å，b= 9.5758(13)Å，c= 20.821(3)Å；α=90°，β= 104.301(5)°，γ= 90°。
3. the visible light totally absorbing cadmium coordination polymer according to claim 2, wherein: the crystal framework of the cadmium coordination polymer HGCP-14 is internally provided with a one-dimensional chain structure formed by PTA ligand and cadmium ions, adjacent chains are piled together through intermolecular force, dppz ligand is chelate end group coordination, and finally a three-dimensional supermolecule porous framework structure is formed;
cd (II) adopts seven coordination, and is respectively matched with two PTAs from different PTAs 2- Four carboxyl oxygen atoms of the ligand, two pyridine nitrogen atoms of one dppz ligand and 1 water molecule coordinate to form a pentagonal bipyramid geometric configuration; adjacent Cd (II) passes through PTA 2– The ligand carboxyl oxygen atoms are coordinately connected to form a one-dimensional chain structure extending along the direction y of the c axis, and pyridine nitrogen atoms on dppz ligands are distributed on two sides of the one-dimensional chain in an end group chelating coordination mode and are distributed in an antiparallel mode;
the chains are overlapped and arranged along an a axis and a b axis by ABAB to form a three-dimensional supermolecule framework structure, a one-dimensional rectangular channel is formed along the b axis, and free TTF guest molecules are arranged in the channel.
4. A method for preparing the visible light total absorption cadmium coordination polymer according to claims 1-3, wherein the method comprises the following steps:
the method specifically comprises the following steps:
1) The organic ligand dppz, H 2 PTA, cadmium nitrate and corresponding guest TTF molecules are added into a mixed solvent of DMF, methanol, water and fluoboric acid and are uniformly mixed;
2) Sealing the obtained mixed liquid, performing solvothermal reaction at 80-120 ℃ for 24-72 hours, and naturally cooling to room temperature to obtain black brown long strip crystals;
3) And washing the crystal with DMF and drying to obtain the coordination polymer HGCP-14 with light absorption performance.
5. The method for preparing the visible light total absorption cadmium coordination polymer according to claim 4, wherein the method comprises the following steps:
the mol ratio of dppz, PTA, cadmium nitrate and guest molecules in the step 1) is 1:1-2:1-3:0.5-1;
the volume ratio of DMF, methanol, water and fluoroboric acid is 10-20:10-20:0.5-1;
the ratio of dppz to the amount of the mixed solvent was 0.05 mmol: 5-10 ml.
6. Use of the visible light fully absorbing cadmium coordination polymer according to any one of claims 1 to 5 as light absorbing material.
7. The use according to claim 6, wherein: the cadmium coordination polymer has an absorption effect on visible light and near-infrared short-wave light waves within the range of 350-1000nm, and has a lower forbidden bandwidth value of 1.453eV.
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| Application Number | Priority Date | Filing Date | Title |
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