CN106866990B - A kind of ruthenium coordination polymer with visible light catalytic reduction of CO2 performance and preparation method and use thereof - Google Patents
A kind of ruthenium coordination polymer with visible light catalytic reduction of CO2 performance and preparation method and use thereof Download PDFInfo
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- CN106866990B CN106866990B CN201710080908.1A CN201710080908A CN106866990B CN 106866990 B CN106866990 B CN 106866990B CN 201710080908 A CN201710080908 A CN 201710080908A CN 106866990 B CN106866990 B CN 106866990B
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- 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
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- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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Abstract
The present invention relates to one kind, and there is visible light catalytic to restore CO2The ruthenium coordination polymer of performance and its synthesis and purposes.The method have the advantages that: polymer crystal material is readily synthesized, and simple solvent heat can be obtained, and crystalline size size and morphology controllable；Crystalline material obtained has many advantages, such as the light absorption of wide scope in ultraviolet visible light region, and light is stablized；The crystalline material shows excellent visible light catalytic reduction CO2Effect, phototransformation efficiency are 110 μm of ol (g of Cat.)‑1h‑1.The present invention is able to achieve green catalysis for the effective use sun and provides experimental technique basis.
Description
Technical field
The present invention relates to one kind, and there is visible light catalytic to restore CO2The ruthenium coordination polymer of performance and its synthesis and purposes.
Background technique
By CO2Caused greenhouse effects are got worse, and how stability contorting atmospheric greenhouse gas has become research hotspot,
And the concern for each disciplinary study person such as cause environment, the energy, physics, chemistry.CO2It is not easily-activated since inertia is big, so that its
Solidification and conversion are restricted, and to complete CO2Conversion need to consume many energy and resource, therefore, develop the CO of low energy consumption2
Conversion has great importance.Photocatalysis can carry out at normal temperatures and pressures, not need to consume a large amount of additional energy, operating condition
It is simple and easy to control, and be a kind of method that can efficiently use solar energy.
Referring to the photosynthesis of green plants, in light-catalyzed reaction system, it is necessary to introduce effective photosensitizer and be urged with light
Agent.Generally there is multiple energy level transition in photosensitizer, so as to absorb the visible light of wide scope, formed to have and be lived under light illumination
The excitation state of property, generally includes metallo phthalocyanine, the more pyridine compounds and theirs of metal and metalloporphyrin cyclics
Deng.Herein, we introduce sensitization and the difunctional Ru compound of catalysis of more pyridines, are had with the hot method of simple solvent
Excellent visible light catalytic restores CO2The ruthenium coordination polymer material of performance.
Summary of the invention
The purpose of the present invention is to provide one kind, and there is visible light catalytic to restore CO2The ruthenium coordination polymer of performance.
It is another object of the present invention to provide one kind, and there is visible light catalytic to restore CO2The ruthenium coordination polymer of performance
Preparation method.
It is another object of the present invention to provide one kind, and there is visible light catalytic to restore CO2The ruthenium coordination polymer of performance
Purposes.
Technical scheme is as follows: there is one kind visible light catalytic to restore CO2The ruthenium coordination polymer of performance, it is described
Ruthenium coordination polymer material structural formula be { Gd2[Ru(dcbpy)3]}·2ClO4 -, wherein the dcbpy is 2,2- connection
Pyridine -4,4- dicarboxylic acid radical ion.
Further, a kind of ruthenium metal coordinating polymer belongs to monoclinic system C2/c space group, its unit cell ginseng
Number are as follows:α=90, β=114.12, γ
=90, V=6311 (4).
There is one kind visible light catalytic to restore CO2The preparation method of the ruthenium coordination polymer of performance, using solvent heat legal system
The standby ruthenium coordination polymer, specifically comprises the following steps:
(1) Ru (H is prepared2dcbpy)3Cl2
By RuCl3And H2Dcbpy is added in reaction kettle, and HCl solution is then added in a kettle, then ultrasound 30 minutes
More than, make RuCl3And H2Dcbpy sufficiently dissolves；Reaction kettle is put into baking oven later, the temperature that baking oven is arranged is 180~200
DEG C, reaction 3 days or more, solid is finally precipitated, is filtered, washed, dries, obtains Ru (H2dcbpy)3Cl2；Wherein, described
RuCl3、H2The molar ratio of dcbpy and HCl is 1:2~3:1000~1200；
(2) { Gd is prepared2[Ru(dcbpy)3]}·2ClO4 -
By Gd (NO3)3With Ru (H2dcbpy)3Cl2Reaction flask is added at room temperature, then adds HClO4Solution, ultrasound
30 minutes or more, make Gd (NO3)3With Ru (H2dcbpy)3Cl2Sufficiently dissolution is finally putting into 70~120 DEG C of baking ovens and reacts 5~10
After it, the ruthenium metal coordinating polymer can be obtained, wherein the Gd (NO3)3、Ru(H2dcbpy)3Cl2With HClO4
Molar ratio is 1~2:1~2:80~120.
The concentrated hydrochloric acid that the HCl solution is 35%；The HClO4The concentration of solution is 6mol/L.
There is one kind visible light catalytic to restore CO2The purposes of the ruthenium coordination polymer of performance, it is characterised in that: the ruthenium
Coordination polymer is used to prepare visible light catalytic reduction CO2Out-phase photocatalyst material.
It is a kind of to realize that visible light catalytic restores CO using visible light2The material of performance, it is characterised in that: the utilization can
Light-exposed realization visible light catalytic restores CO2The material of performance is prepared by the New Ruthenium metal organic coordination polymer.
The beneficial effects of the present invention are:
(1) { Gd is grown2[Ru(dcbpy)3]}·2ClO4 -Crystal is readily synthesized, and simple solvent heat can be obtained, and
Crystalline size size and morphology controllable；
(2) crystalline material obtained has many advantages, such as the light absorption of wide scope in ultraviolet visible light region, and light is stablized；
(3) crystalline material obtained shows excellent visible light catalytic reduction CO2Effect, phototransformation efficiency are 110 μ
mol(g of Cat.)-1h-1.The present invention is able to achieve green catalysis for the effective use sun and provides experimental technique basis.
Detailed description of the invention
Fig. 1 is { Gd in the embodiment of the present invention 12[Ru(dcbpy)3]}·2ClO4 -The simulation powder xrd pattern of crystal.
Fig. 2 is { Gd in the embodiment of the present invention 12[Ru(dcbpy)3]}·2ClO4 -The test powders XRD diagram of crystal.
Fig. 3 is { Gd in the embodiment of the present invention 22[Ru(dcbpy)3]}·2ClO4 -The visible absorption spectrum figure of crystal.
Fig. 4 is { Gd in the embodiment of the present invention 32[Ru(dcbpy)3]}·2ClO4 -The photocatalysis effect figure of crystal.
Specific embodiment:
The present invention is further described below with reference to examples and drawings.As known to those skilled in the art, following embodiments are not
It is limiting the scope of the invention, any improvements and changes made on the basis of the present invention are all in protection model of the invention
Within enclosing.
Case study on implementation 1
Using solvent structure ruthenium metal organic coordination polymer, its steps are as follows:
(1)Ru(H2dcbpy)3Cl2
Weigh 1 mole of RuCl3With the H of 2.5 molar parts2Dcbpy is added in reaction kettle, is then added in a kettle again
1100 moles of concentrated hydrochloric acid solution then ultrasound 30 minutes or more, dissolves it sufficiently；Finally reaction kettle is put into baking oven,
It is 190 DEG C that temperature, which is arranged, reaction 3 days or more.
Solid is finally precipitated, is filtered, washed, dries, obtains Ru (dcbpy)3Cl2；
Reaction equation is as follows
RuCl3+3H2dcbpy→Ru(H2dcbpy)3Cl2+Cl-
(2){Gd2[Ru(dcbpy)3]}·2ClO4 -
With 2 moles of Gd (NO3)3With 1 mole of Ru (H2dcbpy)3Cl2For raw material, reaction flask is added at room temperature, then adds
100 moles of HClO4Solution after ultrasonic 30min or more, dissolves it sufficiently.It is finally putting into 90 DEG C of baking ovens and reacts.
After reaction 7 days, ruthenium metal coordinating polymer material { Gd can be obtained2[Ru(dcbpy)3]}·2ClO4 -Crystal.
Reaction equation is as follows
2Gd(NO3)3+Ru(H2dcbpy)3Cl2+2HClO4→
{Gd2[Ru(dcbpy)3]}·2ClO4 -+6NO3 -+8H+
The concentrated hydrochloric acid that the HCl solution is 35%；The HClO4The concentration of solution is 6mol/L.
Single Crystal X-ray test is carried out to obtained product, obtains the X-ray analogue spectrums of monocrystalline as shown in Figure 1, Fig. 2 is
The test powders XRD diagram of crystal, Fig. 2 and Fig. 1 coincide.
Case study on implementation 2
Using solvent structure ruthenium metal organic coordination polymer, its steps are as follows:
(1)Ru(H2dcbpy)3Cl2
Weigh 1 mole of RuCl3With 2 moles of H2Dcbpy is added in reaction kettle, is then added 1000 in a kettle again and rubs
Your concentrated hydrochloric acid solution then ultrasound 30 minutes or more, dissolves it sufficiently；Finally reaction kettle is put into baking oven, setting temperature
Degree is 180 DEG C, reaction 3 days or more.
Solid is finally precipitated, is filtered, washed, dries, obtains Ru (dcbpy)3Cl2；
Reaction equation is as follows
RuCl3+3H2dcbpy→Ru(H2dcbpy)3Cl2+Cl-
(2){Gd2[Ru(dcbpy)3]}·2ClO4 -
With 1 mole of Gd (NO3)3With 1 mole of Ru (H2dcbpy)3Cl2For raw material, reaction flask is added at room temperature, then adds
80 moles of HClO4Solution after ultrasonic 30min or more, dissolves it sufficiently.It is finally putting into 70 DEG C of baking ovens and reacts.
After reaction 10 days, ruthenium metal coordinating polymer material { Gd can be obtained2[Ru(dcbpy)3]}·2ClO4 -Crystal.
Reaction equation is as follows
2Gd(NO3)3+Ru(H2dcbpy)3Cl2+2HClO4→
{Gd2[Ru(dcbpy)3]}·2ClO4 -+6NO3 -+8H+
The concentrated hydrochloric acid that the HCl solution is 35%；The HClO4The concentration of solution is 6mol/L.
Single Crystal X-ray test is carried out to obtained product, obtains the X-ray analogue spectrums of monocrystalline as shown in Figure 1, Fig. 2 is
The test powders XRD diagram of crystal, Fig. 2 and Fig. 1 coincide.
Case study on implementation 3
Using solvent structure ruthenium metal organic coordination polymer, its steps are as follows:
(1)Ru(H2dcbpy)3Cl2
Weigh 1 part of RuCl3With 3 moles of H2Dcbpy is added in reaction kettle, is then added 1200 moles in a kettle again
Concentrated hydrochloric acid solution, then ultrasound 30 minutes or more, dissolves it sufficiently；Finally reaction kettle is put into baking oven, temperature is set
It is 200 DEG C, reaction 3 days or more.
Solid is finally precipitated, is filtered, washed, dries, obtains Ru (dcbpy)3Cl2；
Reaction equation is as follows
RuCl3+3H2dcbpy→Ru(H2dcbpy)3Cl2+Cl-
(2){Gd2[Ru(dcbpy)3]}·2ClO4 -
With 1 mole of Gd (NO3)3With 2 moles of Ru (H2dcbpy)3Cl2For raw material, reaction flask is added at room temperature, then adds
120 moles of HClO4Solution after ultrasonic 30min or more, dissolves it sufficiently.It is finally putting into 120 DEG C of baking ovens and reacts.
After reaction 5 days, ruthenium metal coordinating polymer material { Gd can be obtained2[Ru(dcbpy)3]}·2ClO4 -Crystal.
Reaction equation is as follows
2Gd(NO3)3+Ru(H2dcbpy)3Cl2+2HClO4→
{Gd2[Ru(dcbpy)3]}·2ClO4 -+6NO3 -+8H+
The concentrated hydrochloric acid that the HCl solution is 35%；The HClO4The concentration of solution is 6mol/L.
Single Crystal X-ray test is carried out to obtained product, obtains the X-ray analogue spectrums of monocrystalline as shown in Figure 1, Fig. 2 is
The test powders XRD diagram of crystal, Fig. 2 and Fig. 1 coincide.
Optical performance test
The visible light absorption capacity of obtained polymer material is measured by its visible absorption spectrum.Utilize Perkin-
Light absorption of the Elmer Lambda 900UV/vis spectrometer test material from 300 to 650nm.If Fig. 3 is the present invention
Ruthenium metal coordinating polymer { Gd2[Ru(dcbpy)3]}·2ClO4 -Optical absorption spectra, material shows from 300 to 620nm wave band
Good absorption ability illustrates there is good visible absorption, realizes that visible light catalytic provides experimental basis for it.
Photocatalysis performance test
Carry out visible light catalytic experiment with the irradiation of xenon lamp visible light wave range, 50mg catalyst in catalystic converter system into
Row 6 hours of reaction detect product HCOO using ion chromatograph (881Compact IC pro, Metrosep)-Amount (figure
4), photo catalytic reduction CO2Generate the HCOO of 33umol–, to calculate phototransformation efficiency, phototransformation efficiency value is 110 μm of ol (g
of Cat.)-1h-1。
Above-mentioned specific embodiment is only explained in detail technical solution of the present invention, the present invention not only only office
Be limited to above-described embodiment, it will be understood by those skilled in the art that it is all according to above-mentioned principle and spirit on the basis of the present invention
It improves, substitution, it all should be within protection scope of the present invention.
Claims (7)
1. there is one kind visible light catalytic to restore CO2The ruthenium coordination polymer of performance, it is characterised in that: the ruthenium coordination polymerization
The structural formula of object is { Gd2[Ru(dcbpy)3]}·2ClO4 -, wherein the dcbpy is 2,2- bipyridyl -4,4- dicarboxylic acids
Radical ion.
2. a kind of ruthenium coordination polymer according to claim 1, it is characterised in that: the ruthenium coordination polymer belongs to list
Oblique system C2/c space group.
3. a kind of ruthenium coordination polymer according to claim 2, it is characterised in that: the unit cell of the ruthenium coordination polymer
Parameter are as follows:α=90, β=114.12, γ=
90, V=6311 (4).
4. a kind of preparation method of ruthenium coordination polymer described in any one of -3 according to claim 1, it is characterised in that: adopt
With the solvent-thermal method preparation ruthenium coordination polymer, specifically comprise the following steps:
(1) Ru (H is prepared2dcbpy)3Cl2
By RuCl3And H2Dcbpy is added in reaction kettle, and HCl solution is then added in a kettle, and then ultrasound 30 minutes or more,
Make RuCl3And H2Dcbpy sufficiently dissolves；Reaction kettle is put into baking oven later, the temperature that baking oven is arranged is 180~200 DEG C, instead
It answers 3 days or more, after solid is precipitated, is then filtered, washed and dries, obtain Ru (H2dcbpy)3Cl2；Wherein, the RuCl3、
H2The molar ratio of dcbpy and HCl is 1:2~3:1000~1200；
(2) { Gd is prepared2[Ru(dcbpy)3]}·2ClO4 -
By Gd (NO3)3With Ru (H2dcbpy)3Cl2Reaction flask is added at room temperature, then adds HClO4Solution, 30 points of ultrasound
More than clock, make Gd (NO3)3With Ru (H2dcbpy)3Cl2Sufficiently dissolution, is finally putting into 70~120 DEG C of baking ovens and reacts 5~10 days
Afterwards to get arrive the ruthenium metal coordinating polymer, wherein the Gd (NO3)3、Ru(H2dcbpy)3Cl2With HClO4Mole
Than for 1~2:1~2:80~120.
5. a kind of preparation method of ruthenium coordination polymer according to claim 4, it is characterised in that: the HCl solution
In HCl mass percentage concentration be 35%；The HClO4HClO in solution4Concentration be 6mol/L.
6. a kind of purposes of ruthenium coordination polymer described in any one of -3 according to claim 1, it is characterised in that: described
Ruthenium coordination polymer be used to prepare visible light catalytic reduction CO2Out-phase photocatalyst material.
7. a kind of realize that visible light catalytic restores CO using visible light2The material of performance, it is characterised in that: described using visible
Light realizes that visible light catalytic restores CO2The material of performance ruthenium coordination polymer system as described in any one of claim 1-3
It is standby to form.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001032665A2 (en) * | 1999-11-01 | 2001-05-10 | Fluorrx, Inc. | New ruthenium metal ligand complexes |
| CN101851255A (en) * | 2009-04-01 | 2010-10-06 | 索尼株式会社 | The manufacture method of ruthenium complex |
| CN103044494A (en) * | 2013-01-21 | 2013-04-17 | 中国科学院福建物质结构研究所 | Ruthenium metal organic polymer luminous material and synthesis and application thereof |
| CN103044495A (en) * | 2013-01-21 | 2013-04-17 | 中国科学院福建物质结构研究所 | Ruthenium luminous material and synthesis and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001032665A2 (en) * | 1999-11-01 | 2001-05-10 | Fluorrx, Inc. | New ruthenium metal ligand complexes |
| CN101851255A (en) * | 2009-04-01 | 2010-10-06 | 索尼株式会社 | The manufacture method of ruthenium complex |
| CN103044494A (en) * | 2013-01-21 | 2013-04-17 | 中国科学院福建物质结构研究所 | Ruthenium metal organic polymer luminous material and synthesis and application thereof |
| CN103044495A (en) * | 2013-01-21 | 2013-04-17 | 中国科学院福建物质结构研究所 | Ruthenium luminous material and synthesis and application thereof |
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