CN113058649A - Graphene phthalocyanine composite material and preparation method and application thereof - Google Patents
Graphene phthalocyanine composite material and preparation method and application thereof Download PDFInfo
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- CN113058649A CN113058649A CN202110281781.6A CN202110281781A CN113058649A CN 113058649 A CN113058649 A CN 113058649A CN 202110281781 A CN202110281781 A CN 202110281781A CN 113058649 A CN113058649 A CN 113058649A
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- phthalocyanine
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 phthalocyanine compound Chemical class 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000007363 ring formation reaction Methods 0.000 claims description 15
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000007385 chemical modification Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 53
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 30
- 239000011701 zinc Substances 0.000 description 23
- 229910052725 zinc Inorganic materials 0.000 description 23
- 150000003751 zinc Chemical class 0.000 description 20
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical class OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 18
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 18
- 150000002696 manganese Chemical class 0.000 description 18
- 239000011572 manganese Substances 0.000 description 18
- 229910052748 manganese Inorganic materials 0.000 description 18
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical class ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
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- 230000008569 process Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
- B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
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- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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Abstract
The invention relates to a graphene phthalocyanine composite material and a preparation method and application thereof. The preparation raw materials comprise reduced graphene and phthalocyanine compound; the phthalocyanine compound has a structure shown in a formula I or a formula II; m1And M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；R1And R2Are each independently selected from-NH2or-NO2(ii) a The above-mentionedThe mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10). The two have strong binding force. The used phthalocyanine material is easy to prepare, the cost of raw materials is low, the graphene and the phthalocyanine can be tightly combined together without additional chemical modification, and the method has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of graphene composite materials, in particular to a graphene phthalocyanine composite material and a preparation method and application thereof.
Background
Since the advent, graphene has attracted extensive research interest due to its two-dimensional structure and excellent optical and electrical properties. Graphene consists of a single layer or a few layers of carbon atoms, the atoms in the layers are connected by strong covalent bonds, and the layers are stacked by van der waals force. Compared with a bulk material, the atom utilization rate of the two-dimensional graphene is obviously improved; the thickness at the atomic level is favorable for the deep research of the reaction process; the regulation and control of energy band structure and electrical characteristics can be realized through thickness control and element doping; the larger lateral dimension gives it a higher specific surface area, which helps to expose more active sites, thus increasing catalytic efficiency. The excellent characteristics show good application prospects in the fields of electronics, energy conversion and storage, photoelectrocatalysis and the like. However, the catalytic activity of pure graphene is still low, and it needs to be doped with hetero atoms or compounded with metal particles, oxides and metal organic complexes to improve the catalytic activity.
In recent years, graphene phthalocyanine composite materials as a novel electronic material and photocatalyst become a research hotspot. The phthalocyanine is a compound with a large-pi-codlot system, has excellent photoelectric response and semiconductor properties, and can realize systematic adjustment of physical, chemical and electronic properties of materials by methods of functional group modification, central metal change and the like so as to meet the requirements of practical application; the graphene is a photoelectric material with excellent performance, and the graphene and the photoelectric material are compounded, so that the phthalocyanine material can be effectively dispersed on the surface of the graphene, and the problem that phthalocyanine molecules are easy to agglomerate is solved; meanwhile, the two can form an electron donor-acceptor system, and electrons generated by photo-excitation of phthalocyanine molecules are transferred to the graphene sheet layer, so that the electrons are rapidly separated from the donor. In the field of photoelectrocatalysis, separation of molecules (e.g. O) whose electrons are transferred to a mediator2、H2O2Etc.) to form free radicals or negative ions, and the free radicals or negative ions react with reactants to promote oxidation or reduction reaction, thereby greatly improving the catalytic activity of the material; in the electronic field, the process is beneficial to the separation of carriers (electrons and holes), and the efficiency of the device can be effectively improved.
At present, the preparation method of the graphene phthalocyanine composite material is still more complicated and complicated in process, for example, the surface of graphene needs to be functionalized, or some special functional groups are introduced into a phthalocyanine ring to improve the binding force between the graphene and the phthalocyanine ring, so that the preparation cost of the material is improved by such operation, and the popularization and the application of the material are not facilitated. Therefore, a preparation method which is simple, low in cost and suitable for large-scale production needs to be found urgently.
Disclosure of Invention
Based on the graphene phthalocyanine composite material, the used phthalocyanine material is easy to prepare, the raw material cost is low, and the graphene and phthalocyanine material are strong in binding force. The preparation method has simple steps and low cost, can tightly combine the graphene and the phthalocyanine together without carrying out additional chemical modification on the graphene or the phthalocyanine material, can realize the adsorption of phthalocyanine nanoparticles with different sizes and monomolecular phthalocyanine on the surface of the graphene by simple process adjustment, can realize large-scale production, and has wide application prospect.
Specifically, the technical scheme of the invention is as follows:
a graphene phthalocyanine composite material is prepared from reduced graphene and a phthalocyanine compound; the phthalocyanine compound has a structure shown in a formula I or a formula II;
M1and M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；
R1And R2Are each independently selected from-NH2or-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10).
In one embodiment, the phthalocyanine compound has a structure shown in formula I, R1Are all-NH2Or R1Are all-NO2(ii) a The mass ratio of the reduced graphene to the phthalocyanine compound is (1-2): (2-5).
In one embodiment, the phthalocyanine compound has a structure shown in formula II, R2Are all-NH2Or R2Are all-NO2(ii) a The mass ratio of the reduced graphene to the phthalocyanine compound is (1-2): (2-5).
The invention also provides a preparation method of the graphene phthalocyanine composite material, which comprises the following steps:
mixing an organic solvent, a phthalocyanine compound and reduced graphene;
the phthalocyanine compound has a structure shown in a formula I or a formula II;
M1and M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；
R1And R2Are each independently selected from-NH2or-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10).
In one embodiment, the preparation method of the graphene phthalocyanine composite material comprises the following steps:
dissolving the phthalocyanine compound in an organic solvent to prepare a phthalocyanine solution;
mixing the reduced graphene with a phthalocyanine solution.
In one embodiment, after the step of mixing the reduced graphene with the phthalocyanine solution, the steps of standing, filtering and drying are further included.
In one embodiment, the standing time is 40-80 h; and/or
During filtering, dichloromethane is also adopted to wash the filter cake; and/or
The drying is natural airing or vacuum drying.
In one embodiment, the organic solvent is selected from N, N-dimethylformamide, dimethylsulfoxide, dichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran or chloroform.
In one embodiment, the concentration of the phthalocyanine compound in the phthalocyanine solution is 0.05mg/mL to 5 mg/mL.
In one embodiment, the phthalocyanine compound has a structure shown in formula I, and R1Are all-NO2The preparation method comprises the following steps:
mixing 4-nitrophthalonitrile, soluble divalent metal salt and quinoline, and carrying out phthalocyanine cyclization under the protection of inert gas to prepare a tetranitro substituted phthalocyanine compound with a structure shown in formula I;
the soluble divalent metal salt is Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+And (3) salt.
Preferably, the molar ratio of the metal ions in the 4-nitrophthalonitrile and the soluble divalent metal salt is (2-4): (0.5 to 1.5).
Preferably, the temperature of the phthalocyanine cyclization reaction is 160-180 ℃ and the time is 2-10 h.
In one embodiment, the phthalocyanine compound has a structure shown in formula I, R1Are all-NH2The preparation method comprisesThe method comprises the following steps:
the tetra-nitro substituted phthalocyanine compound with the structure shown in the formula I is mixed with a reducing agent, and heated and refluxed to prepare the tetra-amino substituted phthalocyanine compound with the structure shown in the formula I.
Preferably, the mass ratio of the tetranitro-substituted phthalocyanine compound with the structure shown in the formula I to the reducing agent is (1-2): (0.5-2). More preferably, the reducing agent for reducing the tetranitro-substituted phthalocyanine compound having the structure shown in formula I is Na2S, the reaction time is 10-20 h.
In one embodiment, the phthalocyanine compound has a structure shown in formula II, and R2Are all-NO2The preparation method comprises the following steps:
mixing 4, 5-dinitrophthalic nitrile, soluble divalent metal salt and quinoline, and carrying out phthalocyanine cyclization under the protection of inert gas to prepare an octanitro-substituted phthalocyanine compound with a structure shown in a formula II;
the soluble divalent metal salt is Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+And (3) salt.
Preferably, the molar ratio of the metal ions in the 4, 5-dinitrophthalic nitrile and the soluble divalent metal salt is (2-4): (0.5 to 1.5).
Preferably, the temperature of the phthalocyanine cyclization reaction is 160-180 ℃ and the time is 2-10 h.
In one embodiment, the phthalocyanine compound has a structure shown in formula II, R2Are all-NH2The preparation method comprises the following steps:
mixing the octa-nitro substituted phthalocyanine compound with the structure shown in the formula II with a reducing agent, and heating and refluxing to prepare the octa-amino substituted phthalocyanine compound with the structure shown in the formula II.
Preferably, the mass ratio of the octanitro-substituted phthalocyanine compound with the structure shown in the formula II to the reducing agent is (1-2): (0.5-2). More preferably, the reducing agent for reducing the octanitro-substituted phthalocyanine compound having the structure shown in formula II is Na2S, reaction time is 10h～20h。
The invention also provides the graphene phthalocyanine composite material prepared by any one of the above embodiments for electrochemical catalytic reduction of CO2And application in photocatalytic degradation of hexavalent chromium ions.
Compared with the prior art, the invention has the following beneficial effects:
the inventor finds that graphene and-NH can be reduced through experience accumulation and a large number of creative experiments of the inventor for years in the field2or-NO2When the substituted phthalocyanine compound is used as a raw material, the bonding force of the substituted phthalocyanine compound and the graphene is strong, the graphene and the phthalocyanine can be tightly bonded together without performing additional chemical modification on the graphene or the phthalocyanine material, the complex steps of preparing the graphene phthalocyanine composite material in the prior art can be avoided, and the raw material cost is low.
In addition, when the graphene phthalocyanine composite material is prepared, the graphene and the phthalocyanine can be tightly combined together without performing additional chemical modification on the graphene or phthalocyanine material, phthalocyanine nanoparticles with different sizes and monomolecular phthalocyanine can be adsorbed on the surface of the graphene by simple process adjustment, and the graphene phthalocyanine composite material can be produced in a large scale and has a wide application prospect.
Drawings
FIG. 1 is a mass spectrum of tetra-amino substituted cobalt phthalocyanine;
FIG. 2 is a mass spectrum of tetranitro substituted cobalt phthalocyanine;
FIG. 3 is a flow chart illustrating the preparation of a graphene phthalocyanine composite according to an embodiment of the present invention;
FIG. 4 is a flow chart of a graphene-phthalocyanine binding force verification experiment in the graphene phthalocyanine composite material of the present invention;
fig. 5 is an ultraviolet-visible absorption spectrum of the graphene-tetraamino substituted cobalt phthalocyanine composite material prepared in example 25 of the present invention;
FIG. 6 shows UV-VIS absorption spectra of tetra-amino substituted cobalt phthalocyanine prepared according to an example of the present invention;
fig. 7 is an ultraviolet-visible absorption spectrum of a graphene-tetranitro substituted cobalt phthalocyanine composite material prepared by an embodiment of the present invention;
FIG. 8 is a UV-VIS absorption spectrum of tetranitro substituted cobalt phthalocyanine prepared in accordance with an embodiment of the present invention;
FIG. 9 shows UV-VIS absorption spectrum of tetranitro-substituted cobalt phthalein DMF solution prepared according to the example of the present invention;
FIG. 10 is a UV-VISIBLE absorption spectrum of a tetra-amino-substituted cobalt phthalein DMF solution prepared according to an example of the present invention;
fig. 11 is a graph of the uv-vis absorption spectrum of reduced graphene used in the examples of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Specifically, the technical scheme of the invention is as follows:
a graphene phthalocyanine composite material is prepared from reduced graphene and a phthalocyanine compound; the phthalocyanine compound has a structure shown in a formula I or a formula II;
M1and M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；
R1And R2Are each independently selected from-NH2or-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10).
In a more preferred embodiment, the phthalocyanine compound has the structure shown in formula I, R1Are all-NH2Or R1Are all-NO2(ii) a The mass ratio of the reduced graphene to the phthalocyanine compound is (1-2): (2-5). This is more advantageous for the close bonding between the phthalocyanine compound and the reduced graphene.
Preferably, for a compound having the structure shown in formula I, and R1Are all-NO2The phthalocyanine compound (tetranitro substituted phthalocyanine compound) of (1), the preparation method comprising the steps of:
mixing 4-nitrophthalonitrile, soluble divalent metal salt and quinoline, and carrying out phthalocyanine cyclization under the protection of inert gas to prepare a tetranitro substituted phthalocyanine compound with a structure shown in formula I;
the soluble divalent metal salt is Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+And (3) salt.
Preferably, the molar ratio of the metal ions in the 4-nitrophthalonitrile and the soluble divalent metal salt is (2-4): (0.5 to 1.5). More preferably, the temperature of the phthalocyanine cyclization reaction is 160-180 ℃ and the time is 2-10 h.
Preferably, for structures having formula I, R1Are all-NH2The preparation method of the tetranitro substituted phthalocyanine compound comprises the following steps:
the tetra-nitro substituted phthalocyanine compound with the structure shown in the formula I is mixed with a reducing agent, and heated and refluxed to prepare the tetra-amino substituted phthalocyanine compound with the structure shown in the formula I.
Preferably, the mass ratio of the tetranitro-substituted phthalocyanine compound with the structure shown in the formula I to the reducing agent is (1-2): (0.5-2). More preferably, the reducing agent for reducing the tetranitro-substituted phthalocyanine compound having the structure shown in formula I is Na2S, the reaction time is 10-20 h.
In a more preferred embodiment thereofThe phthalocyanine compound has a structure shown in formula II, R2Are all-NH2Or R2Are all-NO2(ii) a The mass ratio of the reduced graphene to the phthalocyanine compound is (1-2): (2-5). This is more advantageous for the close bonding between the phthalocyanine compound and the reduced graphene.
Preferably, for a compound having the structure shown in formula II, and R2Are all-NO2The preparation method of the octa-nitro substituted phthalocyanine compound comprises the following steps:
mixing 4, 5-dinitrophthalic nitrile, soluble divalent metal salt and quinoline, and carrying out phthalocyanine cyclization under the protection of inert gas to prepare an octanitro-substituted phthalocyanine compound with a structure shown in a formula II;
the soluble divalent metal salt is Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+And (3) salt.
Preferably, the molar ratio of the metal ions in the 4, 5-dinitrophthalic nitrile and the soluble divalent metal salt is (2-4): (0.5 to 1.5). More preferably, the temperature of the phthalocyanine cyclization reaction is 160-180 ℃ and the time is 2-10 h.
Preferably, for structures having formula II, R2Are all-NH2The preparation method of the octa-amino substituted phthalocyanine compound comprises the following steps:
mixing the octa-nitro substituted phthalocyanine compound with the structure shown in the formula II with a reducing agent, and heating and refluxing to prepare the octa-amino substituted phthalocyanine compound with the structure shown in the formula II.
Preferably, the mass ratio of the octanitro-substituted phthalocyanine compound with the structure shown in the formula II to the reducing agent is (1-2): (0.5-2). More preferably, the reducing agent for reducing the octanitro-substituted phthalocyanine compound having the structure shown in formula II is Na2S, the reaction time is 10-20 h.
The invention also provides a preparation method of the graphene phthalocyanine composite material, which comprises the following steps:
mixing an organic solvent, a phthalocyanine compound and reduced graphene;
the phthalocyanine compound has a structure shown in a formula I or a formula II;
M1and M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；
R1And R2Are each independently selected from-NH2or-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10).
The preparation method has simple steps and low cost, can tightly combine the graphene and the phthalocyanine together without carrying out additional chemical modification on the graphene or the phthalocyanine material, can realize the adsorption of phthalocyanine nanoparticles with different sizes and monomolecular phthalocyanine on the surface of the graphene through simple process adjustment, and can realize large-scale production.
More preferably, the preparation method of the graphene phthalocyanine composite material comprises the following steps:
dissolving the phthalocyanine compound in an organic solvent to prepare a phthalocyanine solution;
mixing the reduced graphene with a phthalocyanine solution.
In one embodiment, after the step of mixing the reduced graphene with the phthalocyanine solution, the steps of standing, filtering and drying are further included.
Preferably, the standing time is 40-80 h; during filtering, dichloromethane is also adopted to wash the filter cake; the drying is natural airing or vacuum drying.
In one embodiment, the organic solvent is selected from N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, or chloroform. Preferably, the organic solvent is DMF or DMSO, and the two solvents have good solubility to the phthalocyanine compound and good dispersibility to the reduced graphene, which is beneficial to uniform adsorption of the phthalocyanine compound on the surface of the reduced graphene.
In one embodiment, the concentration of the phthalocyanine compound in the phthalocyanine solution is 0.05mg/mL to 5 mg/mL. The concentration of the phthalocyanine compound is controlled, so that on one hand, the adsorption state of the phthalocyanine compound on the surface of the reduced graphene is favorably adjusted, the adsorption from a single molecular level to a nanometer level is realized, and meanwhile, the size of phthalocyanine nanoparticles on the surface of the reduced graphene is favorably adjusted through concentration control, and phthalocyanine particles from several nanometers to dozens of nanometers can be obtained on the surface of the reduced graphene; on the other hand, by controlling the concentration, it is possible to prevent the phthalocyanine compound in the solution from being incompletely adsorbed by the reduced graphene due to an excessively high concentration of the phthalocyanine solution, and further prevent the phthalocyanine compound from being unevenly distributed on the surface of the reduced graphene.
The invention also provides the graphene phthalocyanine composite material prepared by any one of the above embodiments for electrochemical catalytic reduction of CO2And application in photocatalytic degradation of hexavalent chromium ions.
The following examples and comparative examples are further described, and the starting materials used in the following examples are commercially available unless otherwise specified.
Example 1
1) 4-Nitrophthalonitrile (1g), CoCl2(0.25g) and 99% quinoline (10mL) were placed in a 50mL single neck round bottom flask and vacuum and argon purged repeatedly to ensure that the flask was oxygen free;
2) heating and refluxing the reaction system at 180 ℃ for 2h under the protection of argon, carrying out phthalocyanine cyclization reaction, and then cooling to room temperature to obtain phthalocyanine cyclization reaction liquid;
3) filtering the phthalocyanine cyclization reaction solution, washing a solid crude product on filter paper by using 100mL of dichloromethane, and then placing the solid crude product in air for airing; placing the collected solid crude product in a Soxhlet extractor, using dichloromethane as a cleaning agent, cleaning until a refluxing solvent is colorless, taking out, and airing; vacuum sublimating to obtain alpha-site tetranitro substituted cobalt phthalocyanine.
The principle of the phthalocyanine cyclization reaction in this example is shown below:
examples 2 to 6
Referring to example 1, 0.25g of cobalt chloride in example 1 was replaced with 0.26g of ZnCl, respectively2、0.25g NiCl2、0.24g FeCl2、0.24g MnCl2、0.26g CuCl2While the other conditions were kept, the α -site tetranitro-substituted zinc phthalocyanine in example 2, the α -site tetranitro-substituted nickel phthalocyanine in example 3, the α -site tetranitro-substituted iron phthalocyanine in example 4, the α -site tetranitro-substituted manganese phthalocyanine in example 5, and the α -site tetranitro-substituted copper phthalocyanine in example 6 were obtained, respectively.
Mass spectrometry results for each compound:
wherein, the calculated value of the alpha position tetranitro substituted cobalt phthalocyanine in the example 1 is 751.02385, and the test value is 751.02557; the mass spectrum is shown in figure 1.
The alpha-tetranitro substituted zinc phthalocyanine in example 2 was calculated as 756.01925 and tested as 756.01885;
the alpha-tetranitro substituted nickel phthalocyanine in example 3 was calculated as 750.02545 and tested as 750.02174;
the alpha-tetranitro-substituted iron phthalocyanine in example 4 was calculated as 748.02505 and tested as 748.02563;
the tetranitro-substituted manganese phthalocyanine at the alpha position in example 5 was calculated as 747.02816 and tested as 747.02435;
the alpha-tetranitro substituted copper phthalocyanine in example 6 was calculated as 755.01971 and tested as 755.01737.
Example 7
1) The alpha-site tetranitro-substituted cobalt phthalocyanine (0.5g) of example 1 and 5% Na were mixed2Placing the S aqueous solution (50mL) into a 100mL single-neck round-bottom flask, heating and refluxing for 15h, and then cooling to room temperature to obtain a phthalocyanine reaction solution;
2) filtering the phthalocyanine cyclization reaction solution obtained in the step 1), washing a solid crude product on filter paper by using 100mL of deionized water and l00mL absolute ethyl alcohol respectively, and then placing in the air for airing; placing the collected solid crude product in a Soxhlet extractor, using dichloromethane as a cleaning agent, cleaning until a refluxing solvent is colorless, taking out, and airing; vacuum sublimating to obtain alpha-site tetra-amino substituted cobalt phthalocyanine.
The principle of the reduction reaction in this example is shown by the following formula:
examples 8 to 12
Referring to example 7, 0.5g of the α -site tetranitro substituted cobalt phthalocyanine in example 7 was replaced with 0.5g of the α -site tetranitro substituted zinc phthalocyanine, 0.5g of the α -site tetranitro substituted nickel phthalocyanine, 0.5g of the α -site tetranitro substituted iron phthalocyanine, 0.5g of the α -site tetranitro substituted manganese phthalocyanine, and 0.5g of the α -site tetranitro substituted copper phthalocyanine, respectively, and the α -site tetraamino substituted zinc phthalocyanine in example 8, the α -site tetraamino substituted nickel phthalocyanine in example 9, the α -site tetraamino substituted iron phthalocyanine in example 10, the α -site tetraamino substituted manganese phthalocyanine in example 11, and the α -site tetraamino substituted copper phthalocyanine in example 12 were obtained, respectively, while keeping other conditions unchanged.
Mass spectrometry results for each compound:
wherein, the calculated value of the alpha-tetra-amino substituted cobalt phthalocyanine in the example 7 is 632.13387, and the test value is 632.13153; the mass spectrum is shown in FIG. 2.
The alpha-tetra-amino substituted zinc phthalocyanine in example 8 was calculated as 636.12254 and tested as 636.12117;
the alpha-tetra-amino substituted nickel phthalocyanine in example 9 was calculated as 630.12874 and tested as 630.12453;
the tetra-amino substituted iron phthalocyanine at the alpha position in example 10 was calculated as 628.12833 and tested as 628.12929;
the tetra-amino substituted manganese phthalocyanine at the alpha position in example 11 was calculated as 627.13144 and tested as 627.13087;
the calculated value of the alpha-tetra-amino substituted copper phthalocyanine in example 12 is 635.12299, and the test value is 635.12185.
Examples 13 to 18
Referring to example 1, 1g of 4-nitrophthalonitrile in examples 1 to 6 was replaced with 1.26g of 4, 5-dinitrophthalodinitrile, and the α -octanitro substituted cobalt phthalocyanine in example 13, the α -octanitro substituted zinc phthalocyanine in example 14, the α -octanitro substituted nickel phthalocyanine in example 15, the α -octanitro substituted iron phthalocyanine in example 16, the α -octanitro substituted manganese phthalocyanine in example 17 and the α -octanitro substituted copper phthalocyanine in example 18 were obtained, respectively, while maintaining the other conditions.
Mass spectrometry results for each compound:
wherein, the calculated value of the alpha position octanitro substituted cobalt phthalocyanine in the example 13 is 930.96362, and the test value is 930.96115;
the octanitro-substituted zinc phthalocyanine in the alpha position in example 14 was calculated as 935.95956 and tested as 935.95001;
the octanitro-substituted nickel phthalocyanine in the alpha position in example 15 was calculated as 929.96577 and tested as 929.96731;
the octanitro-substituted iron phthalocyanine at the alpha position in example 16 was calculated as 927.96536 and tested as 927.96977;
the octanitro-substituted manganese phthalocyanine in the alpha position in example 17 was calculated as 926.96847 and tested as 926.96355;
the calculated value of the alpha-position octanitro-substituted copper phthalocyanine in example 18 is 934.96002, and the test value is 934.95877.
Examples 19 to 24
Referring to example 7, 0.5g of the α -site tetranitro substituted cobalt phthalocyanine in example 7 was replaced with 0.5g of the α -site octanitro substituted cobalt phthalocyanine, 0.5g of the α -site octanitro substituted zinc phthalocyanine, 0.5g of the α -site octanitro substituted nickel phthalocyanine, 0.5g of the α -site octanitro substituted iron phthalocyanine, 0.5g of the α -site octanitro substituted manganese phthalocyanine, and 0.5g of the α -site octanitro substituted copper phthalocyanine, and the α -site octaamino substituted cobalt phthalocyanine in example 19, the α -site octaamino substituted zinc phthalocyanine in example 20, the α -site octaamino substituted nickel phthalocyanine in example 21, the α -site octaamino substituted iron phthalocyanine in example 22, the α -site octaamino substituted manganese phthalocyanine in example 23, and the α -site octaamino substituted copper phthalocyanine in example 24 were obtained, respectively, while maintaining the other conditions.
Mass spectrometry results for each compound:
wherein, the calculated value of the alpha position octa-amino substituted cobalt phthalocyanine in the example 19 is 691.17019, and the test value is 961.17535;
the zinc phthalocyanine substituted with the octamino group at the α -position in example 20 was calculated as 696.16613 and tested as 696.16775;
the calculated value of the alpha-position octamino-substituted nickel phthalocyanine in example 21 is 690.17233, and the test value is 690.17537;
the calculated value of the alpha-position octamino-substituted iron phthalocyanine in example 22 is 688.17193, and the test value is 688.17339;
the calculated value of the alpha-position octamino-substituted manganese phthalocyanine in example 23 is 687.17503, and the test value is 687.17115;
the calculated value of the alpha-position octamino-substituted copper phthalocyanine in example 24 is 695.16659, and the test value is 695.16977.
Example 25
The operation flow of this embodiment is shown in fig. 3:
dissolving 10mg of alpha-tetra-amino substituted cobalt phthalocyanine prepared in the step 7 in 20mL of DMF, transferring the solution to a 50mL volumetric flask after the alpha-tetra-amino substituted cobalt phthalocyanine is completely dissolved, and diluting the solution to a scale with DMF to obtain a 0.2mg/mL tetra-amino substituted cobalt phthalocyanine DMF solution which is dark green;
weigh 20mg of reduced graphene (rGO, commercially available) into a glass bottle;
transferring 10mL of tetra-amino substituted cobalt phthalocyanine DMF solution to a glass bottle filled with rGO to prepare graphene phthalocyanine dispersion liquid;
standing the graphene phthalocyanine dispersion liquid for 48 hours at normal temperature to enable most of the graphene phthalocyanine composite material to be precipitated to the bottom of the bottle;
and filtering the graphene phthalocyanine dispersion liquid, washing the solid on the filter paper by using dichloromethane, and airing in the air to obtain the graphene-tetraamino substituted cobalt phthalocyanine composite material.
Examples 26 to 48
Referring to example 25, the 0.2mg/mL tetra-amino-substituted cobalt phthalocyanine DMF solution of example 25 was replaced with 0.2mg/mL tetra-amino-substituted zinc phthalocyanine DMF solution, 0.2mg/mL tetra-amino-substituted nickel phthalocyanine DMF solution, 0.2mg/mL tetra-amino-substituted iron phthalocyanine DMF solution, 0.2mg/mL tetra-amino-substituted manganese phthalocyanine DMF solution, 0.2mg/mL tetra-amino-substituted copper phthalocyanine DMF solution, 0.2mg/mL tetra-nitro-substituted cobalt phthalocyanine DMF solution, 0.2mg/mL tetra-nitro-substituted zinc phthalocyanine DMF solution, 0.2mg/mL tetra-nitro-substituted nickel phthalocyanine DMF solution, 0.2mg/mL tetra-nitro-substituted iron phthalocyanine DMF solution, 0.2mg/mL tetra-nitro-substituted manganese phthalocyanine DMF solution, 0.2mg/mL tetra-nitro-substituted copper phthalocyanine DMF solution, 0.2mg/mL octaamino-substituted cobalt phthalocyanine DMF solution, 0.2mg/mL octa-substituted zinc phthalocyanine DMF solution, 0.2 mg/octa-amino-substituted zinc phthalocyanine DMF solution, 0.2mg/mL octamino-substituted nickel phthalocyanine DMF solution, 0.2mg/mL octamino-substituted iron phthalocyanine DMF solution, 0.2mg/mL octamino-substituted manganese phthalocyanine DMF solution, 0.2mg/mL octaamino-substituted copper phthalocyanine DMF solution, 0.2mg/mL octanitro-substituted cobalt phthalocyanine DMF solution, 0.2mg/mL octanitro-substituted zinc phthalocyanine DMF solution, 0.2mg/mL octanitro-substituted nickel phthalocyanine DMF solution, 0.2mg/mL octanitro-substituted iron phthalocyanine DMF solution, 0.2mg/mL octanitro-substituted manganese phthalocyanine DMF solution, 0.2mg/mL octanitro-substituted copper phthalocyanine DMF solution, and reduced graphene, tetraamino-substituted zinc phthalocyanine, tetraamino-substituted nickel phthalocyanine, tetraamino-substituted iron phthalocyanine, tetraamino-substituted manganese phthalocyanine, tetraamino-substituted copper phthalocyanine, tetranitro-substituted cobalt, tetranitro-substituted zinc phthalocyanine, tetraamino-substituted nickel phthalocyanine, 0.2mg/mL octanitro-substituted copper phthalocyanine DMF solution are prepared respectively by keeping other conditions unchanged, Tetranitro substituted nickel phthalocyanine, tetranitro substituted iron phthalocyanine, tetranitro substituted manganese phthalocyanine, tetranitro substituted copper phthalocyanine, octaamino substituted cobalt phthalocyanine, octaamino substituted zinc phthalocyanine, octaamino substituted nickel phthalocyanine, octaamino substituted iron phthalocyanine, octaamino substituted manganese phthalocyanine, octaamino substituted copper phthalocyanine, octanitro substituted cobalt phthalocyanine, octanitro substituted zinc phthalocyanine, octanitro substituted nickel phthalocyanine, octanitro substituted iron phthalocyanine, octanitro substituted manganese phthalocyanine, and octanitro substituted copper phthalocyanine.
Example 49
Referring to example 25, the 0.2mg/mL tetra-amino substituted cobalt phthalocyanine DMF solution in example 25 was substituted for the 5mg/mL tetra-amino substituted zinc phthalocyanine DMF solution.
Example 50
Referring to example 25, 10mg of the tetraamino-substituted cobalt phthalein in example 25 was replaced with 100mg of the tetraamino-substituted zinc phthalocyanine.
Comparative example 1
Referring to example 25, a graphene phthalocyanine composite was prepared by replacing the 0.2mg/mL tetraamino-substituted cobalt phthalocyanine DMF solution in example 25 with 0.2mg/mL cobalt phthalocyanine DMF dispersion, and maintaining the other conditions.
Wherein the structure of the cobalt phthalocyanine compound is as follows:
comparative example 2
Referring to example 25, a graphene phthalocyanine composite was prepared by replacing the 0.2mg/mL tetraamino-substituted cobalt phthalocyanine DMF solution in example 25 with 0.2mg/mL zinc phthalocyanine DMF dispersion, and maintaining the other conditions.
Wherein the structure of the zinc phthalocyanine compound is as follows:
comparative example 3
Referring to example 25, the reduced graphene in example 25 was replaced with graphene oxide, and other conditions were maintained to prepare a graphene phthalocyanine composite.
Test example 1
The method for verifying the binding force between graphene and phthalocyanine compound is shown in fig. 4:
and after the graphene phthalocyanine dispersion liquid is kept stand for 48 hours, most of products are settled to the bottom of a glass bottle, supernatant liquid is taken away, DMF solvent is added, shaking is carried out, the mixture is kept stand for 48 hours, and when most of the products are settled to the bottom of the bottle, the color of the upper clear layer is observed. If the supernatant is colorless and transparent, the phthalocyanine compound combined with the graphene cannot be eluted by DMF, and the firm combination between the graphene and the phthalocyanine compound is fully proved. If the supernatant showed the same color as the phthalocyanine solution (e.g., the tetra-amino-substituted cobalt phthalocyanine DMF solution in example 25 showed dark green), it was suggested that the phthalocyanine compound bound to graphene was eluted by DMF, which is a good indication of poor binding between graphene and phthalocyanine compound.
The graphene phthalocyanine composites of examples 26 to 50 of the present invention and comparative examples 1 to 3 were tested according to the method shown in fig. 2, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, the nitro-or amino-substituted metal phthalocyanine compound can be strongly bound to the reduced graphene, while the non-substituted ortho-phthalocyanine cannot be strongly bound to the reduced graphene; and the nitro-or amino-substituted metal phthalocyanine can be firmly bonded to the reduced graphene but cannot be firmly bonded to the oxidized graphene.
Test example 2
Fig. 5 is an ultraviolet-visible absorption spectrum of the graphene-tetraamino substituted cobalt phthalocyanine composite material prepared in example 25 of the present invention; as can be seen from FIG. 5, the sample shows distinct absorption peaks at 321nm and 745nm, corresponding to the B-band absorption and Q-band absorption of the phthalocyanine material, respectively, indicating the presence of phthalocyanine molecules on the reduced graphene, indicating that the phthalocyanine is successfully combined with the graphene.
FIG. 6 shows UV-VIS absorption spectra of tetra-amino substituted cobalt phthalocyanine prepared according to an example of the present invention; the sample has obvious absorption peaks at 310nm and 728nm, which respectively correspond to the B-band absorption and the Q-band absorption of the phthalocyanine material, and shows that phthalocyanine molecules exist on the reduced graphene, which indicates that the phthalocyanine and the graphene are successfully combined.
Fig. 7 is an ultraviolet-visible absorption spectrum of a graphene-tetranitro substituted cobalt phthalocyanine composite material prepared by an embodiment of the present invention; the sample shows an absorption peak at 720nm, which corresponds to the Q-band absorption of the phthalocyanine material, and shows that phthalocyanine molecules exist on the reduced graphene, indicating that the phthalocyanine and the graphene are successfully combined.
FIG. 8 is a UV-VIS absorption spectrum of tetranitro substituted cobalt phthalocyanine prepared in accordance with an embodiment of the present invention; the sample shows absorption peaks at 314nm and 661nm, which correspond to the B-band and Q-band absorption of phthalocyanine, respectively, indicating the successful synthesis of phthalocyanine material.
FIG. 9 shows UV-VIS absorption spectrum of tetranitro-substituted cobalt phthalein DMF solution prepared according to the example of the present invention; the samples showed absorption peaks at 319nm, and 629nm and 674nm, corresponding to the B-band and Q-band absorption of phthalocyanine, respectively, indicating successful synthesis of phthalocyanine material.
FIG. 10 shows UV-VIS absorption spectrum of tetra-amino-substituted cobalt phthalein DMF solution prepared according to the example of the present invention; the sample shows absorption peaks at 319nm and 709nm, which correspond to the B-band and Q-band absorption of phthalocyanine, respectively, indicating the successful synthesis of phthalocyanine material.
FIG. 11 is a graph of the UV-VIS absorption spectrum of reduced graphene used in embodiments of the present invention; as can be seen from fig. 11, no significant absorption peak was seen in the test range for graphene not complexed with phthalocyanine.
Test example 3
Graphene-tetraaminophthalocyanine composite material prepared in example 25 was used for CO2Electrocatalytic reduction of CO2Reduced to CO, the Faraday efficiency is higher than 90%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The graphene phthalocyanine composite material is characterized in that raw materials for preparing the graphene phthalocyanine composite material comprise reduced graphene and a phthalocyanine compound; the phthalocyanine compound has a structure shown in a formula I or a formula II;
M1and M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；
R1And R2Are each independently selected from-NH2or-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10).
2. The graphene phthalocyanine composite according to claim 1, wherein the phthalocyanine compound has a structure represented by formula I, R1Are all-NH2Or R1Are all-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-2): (2-5).
3. The graphene phthalocyanine composite according to claim 1, wherein the phthalocyanine compound has a structure represented by formula II, R2Are all-NH2Or R2Are all-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-2): (2-5).
4. The preparation method of the graphene phthalocyanine composite material is characterized by comprising the following steps:
mixing an organic solvent, a phthalocyanine compound and reduced graphene;
the phthalocyanine compound has a structure shown in a formula I or a formula II;
M1and M2Are each independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+；
R1And R2Are each independently selected from-NH2or-NO2；
The mass ratio of the reduced graphene to the phthalocyanine compound is (1-5): (2-10).
5. The method for preparing the graphene phthalocyanine composite material according to claim 4, comprising the steps of:
dissolving the phthalocyanine compound in an organic solvent to prepare a phthalocyanine solution;
mixing the reduced graphene with a phthalocyanine solution.
6. The method for preparing a graphene phthalocyanine composite material according to claim 5, further comprising the steps of standing, filtering and drying after the step of mixing the reduced graphene with the phthalocyanine solution; the standing time is 40-80 h; and/or
During filtering, dichloromethane is also adopted to wash the filter cake; and/or
The drying is natural airing or vacuum drying.
7. The method for producing a graphene phthalocyanine composite according to any one of claims 4 to 6, wherein the organic solvent is selected from N, N-dimethylformamide, dimethyl sulfoxide, dichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran or chloroform; the concentration of the phthalocyanine compound in the phthalocyanine solution is 0.05 mg/mL-5 mg/mL.
8. The method for preparing a graphene phthalocyanine composite according to any one of claims 4 to 6, wherein the phthalocyanine compound has a structure represented by formula I, and R is1Are all-NO2The preparation method comprises the following steps:
mixing 4-nitrophthalonitrile, soluble divalent metal salt 1 and quinoline, and carrying out phthalocyanine cyclization under the protection of inert gas to prepare a tetranitro substituted phthalocyanine compound with a structure shown in formula I; and/or
The phthalocyanine compound has a structure shown in formula II, and R2Are all-NO2The preparation method comprises the following steps:
mixing 4, 5-dinitrophthalic nitrile, soluble divalent metal salt 2 and quinoline, and carrying out phthalocyanine cyclization under the protection of inert gas to prepare an octanitro-substituted phthalocyanine compound with a structure shown in a formula II;
the soluble divalent metal salt 1 and the soluble divalent metal salt 2 are respectively and independently selected from Co2+、Zn2+、Ni2+、Fe2+、Mn2+Or Cu2+And (3) salt.
9. The method for preparing a graphene phthalocyanine composite material according to claim 8, wherein the phthalocyanine compound has a structure shown in formula I, R1Are all-NH2The preparation method comprises the following steps:
mixing the tetranitro substituted phthalocyanine compound with the structure shown in the formula I and a reducing agent, and heating and refluxing to prepare the tetraamino substituted phthalocyanine compound with the structure shown in the formula I; and/or
The phthalocyanine compound has a structure shown in formula II, R2Are all-NH2The preparation method comprises the following steps:
mixing the octa-nitro substituted phthalocyanine compound with the structure shown in the formula II with a reducing agent, and heating and refluxing to prepare the octa-amino substituted phthalocyanine compound with the structure shown in the formula II.
10. Graphene phthalocyanine composite material according to any one of claims 1 to 3 or prepared by the preparation method according to any one of claims 4 to 9 in the electrochemical catalytic reduction of CO2And application in photocatalytic degradation of hexavalent chromium ions.
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