CN105688995A - Method for preparing metalloporphyrin-graphene nano composite material under condition of room temperature - Google Patents
Method for preparing metalloporphyrin-graphene nano composite material under condition of room temperature Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- -1 cationic porphyrin Chemical class 0.000 claims abstract description 10
- 238000000862 absorption spectrum Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical group [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001455 metallic ions Chemical class 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
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- 238000011282 treatment Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- MRHHHYZFDDQAQL-UHFFFAOYSA-N 2,3,6,7-tetramethylquinoxaline Chemical compound CC1=C(C)N=C2C=C(C)C(C)=CC2=N1 MRHHHYZFDDQAQL-UHFFFAOYSA-N 0.000 description 29
- 101100361108 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) eas gene Proteins 0.000 description 29
- LRXUJWQJCUIVBG-UHFFFAOYSA-N 4-chloro-6-(trifluoromethyl)-2,1,3-benzothiadiazole Chemical compound C1=C(C(F)(F)F)C=C(Cl)C2=NSN=C21 LRXUJWQJCUIVBG-UHFFFAOYSA-N 0.000 description 12
- 101100449516 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) grg-1 gene Proteins 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- NCAJWYASAWUEBY-UHFFFAOYSA-N 3-[20-(2-carboxyethyl)-9,14-diethyl-5,10,15,19-tetramethyl-21,22,23,24-tetraazapentacyclo[16.2.1.1^{3,6}.1^{8,11}.1^{13,16}]tetracosa-1(21),2,4,6(24),7,9,11,13,15,17,19-undecaen-4-yl]propanoic acid Chemical compound N1C2=C(C)C(CC)=C1C=C(N1)C(C)=C(CC)C1=CC(C(C)=C1CCC(O)=O)=NC1=CC(C(CCC(O)=O)=C1C)=NC1=C2 NCAJWYASAWUEBY-UHFFFAOYSA-N 0.000 description 1
- AIRPQPQNHSLMPG-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin-2-carboxylic acid Chemical compound C(=O)(O)C1=C2NC(=C1)C(=C1C=CC(=N1)C(=C1C=CC(N1)=C(C=1C=CC(N=1)=C2C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 AIRPQPQNHSLMPG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- GFERWFAWHAQLLF-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(N)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical class [N]1C2=CC=C1C=C(N1)C=C(N)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 GFERWFAWHAQLLF-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J31/18—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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention discloses a method for preparing a metalloporphyrin-graphene nano composite material under a condition of room temperature. Rapid preparation of the metalloporphyrin-graphene nano composite material is realized by virtue of utilizing metal ions, porphyrin and graphene as main raw materials in a water solution, and changing the chemical reduction degree of graphene oxide, the molecular structure of cationic porphyrin, the system pH value and the like to regulate the porphyrin ring embedding capability of metal ions. Compared with an existing preparation technology of the metalloporphyrin-graphene nano composite material, the method provided by the invention is capable of realizing a metal ion and porphyrin coordination process without a high temperature condition or a long-time heating reflow process, is environmentally-friendly and mild in preparation condition, simple and convenient to operate, stable in structure and suitable for enlarged preparation and actual production application, and has wide application prospect in the fields of catalytic materials, photoelectric materials and heavy metal ion treatment.
Description
Technical field
The present invention relates to graphene composite material preparation field, specifically, relate to the new green method preparing metalloporphyrin-graphene complex at ambient temperature。
Background technology
Graphene is the former molecular two-dimension nano materials of monolayer carbon, has the premium properties such as high-specific surface area, high-termal conductivity and high conductivity。Along with deepening continuously that Graphene is studied, its functionalization is proposed higher requirement by people, and therefore graphene composite material gets the attention。
In porphyrin ring, two protons are the formation of metalloporphyrin after being replaced by metal, diversified molecule performance can be shown by the substituent group etc. introducing different metal center ion, change on porphyrin ring, all contain the core texture of metalloporphyrin as being widely present in chlorophyll (i.e. magnesium porphyrin) in the functional unit of nature, haemachrome (i.e. iron porphyrin), vitamin B12 (i.e. Cob altporphyrin) etc.。Due to the big π structure of the high conjugation of the good stability of metalloporphyrin, it is possible to as a kind of electronics object, it is possible to assemble with carbon/silicon nano material, oxide-based nanomaterial etc., have tempting application prospect in the field such as catalysis material and photoelectric material。
Graphene has excellent physical and chemical performance, metalloporphyrin has good electron donation and multi-functional tuning capability, can obtain the multifunctional graphite vinyl composite material of Novel series in conjunction with the two feature。Such as Bratche is prepared for the carboxyl tetraphenylporphyrin/graphene oxide composite material being connected with covalent bond at first by esterification, this material has good absorbing properties and optical stability (BaskaranD., MaysJ.W., ZhangX.P., BratcherM.S.J.Am.Chem.Soc, 2005,127:6916 6917)；Chen and Tagmatarchis seminar is prepared for the composite that Amino Porphyrins/graphene oxide is connected by amido link subsequently, and have studied its optical Limiting feature and the application (XuY.F. in fuel sensitization solar battery thereof, LiuZ.B., ChenY.S.Adv.Mater.2009,21:1275-1279；KarousisN., SandanayakaA.S.D., HasobeT.JMater.Chem.2011,21:109-117)；Shi Gaoquan and Ju Xian professor is successively prepared for cationic porphyrin/redox graphene non-covalent complex, and it is applied to the analysis detection (XuY.X. of cadmium ion and chlorite, ZhaoL., BaiH.J.Am.Chem.Soc.2009,131:13490-13497；TuW.W., LeiJP, JuHX.Chem.Eur.J.2010,16:10771-10777)；Graphene oxide/hemoporphyrin complex is applied to photodynamic therapy (GrinceviciuteN., SnopokB., SnitkaV.Chem.Eng.J., 2014,225,577-584) by Grinceviciute etc.；Zhou etc. prepare copper porphyrin/graphene complex and as ammonia gas sensor (ZhouXQ, WangXL, WangB.SensorsandActuatorsB:Chemical, 2014,193:340-348)。The studies above enriches the preparation method and application field of porphyrin-graphene complex greatly。
But, prepare metalloporphyrin-Graphene method at present for first synthesizing metalloporphyrin, prepare metalloporphyrin-graphene complex again, and the condition synthesizing metalloporphyrin all synthesizes under the harsh conditions such as high-temperature heating or long-time backflow, it is significant so finding the green method fast preparing metalloporphyrin-Graphene under a kind of room temperature condition。
Summary of the invention
It is desirable to provide the preparation method of a metalloid porphyrin-graphene complex, the method aqueous solution at ambient temperature realizes the quick preparation of metalloporphyrin-graphene nanocomposite material with metal ion, porphyrin, Graphene for primary raw material, it is not necessary to be heated to reflux process。
Technical scheme is as follows:
A kind of metalloporphyrin-graphene nanocomposite material, its general structure is as follows:
Wherein substituent R is CH3,CH2CH3,(CH2)2CH3,(CH2)3CH3,(CH2)4CH3,(CH2)5CH3,(CH2)3OH,CH2COOCH2CH3,CH2C6H5,CH2C6H4CH3And CH2C6H4NO2In one；
Wherein M is metal ion, it is preferable that Zn2+,Cd2+,Pb2+Or Hg2+；
Wherein Graphene is the graphene oxide of gradient reduction, and carrying out gradient reduction by the amount of adjustment with the reducing agent hydrazine hydrate of graphite oxide alkene reaction can obtain。
The preparation method of above-mentioned metalloporphyrin-graphene nanocomposite material, synthetic route is as follows,
Comprise the steps:
(1) Alder-longer method synthesizing series four pyridylporphyrin, the alkylated reaction synthesizing series cationic porphyrin of recycling N are utilized；This compounds commercialization, it is possible to directly buy；
(2) utilizing Hummers method to prepare graphene oxide, ultrasonic disperse obtains the graphene oxide dispersion of 0.15～1.5mg/mL, gradient reduced after graphene oxide dispersion；
(3) compound concentration is 1～100 μM (namely 10-6～10-4Mol/L) cationic porphyrin aqueous solution, is added dropwise over the graphene oxide dispersion after reduction wherein, shakes up standing, monitored the generation process of porphyrin-graphene complex by uv-visible absorption spectra；
(4) again to porphyrin-graphene complex solution dropping metal ion solution, the substance withdrawl syndrome making complex and metal ion reaches 1:1～5, and (complex concentration is with porphyrin concentration for benchmark, due to Porphyrin Molecule structure, Graphene reducing degree, species of metal ion difference, optimal concentration proportioning also can there are differences), standing is shaken up under room temperature or room temperature condition, when reaching stable red shift by uv-visible absorption spectra monitoring complex, namely obtain metalloporphyrin-graphene nanocomposite material。
Further, in preparation process (2), described gradient reduction is particularly as follows: with 40mL, 0.15mg/mL graphene oxide dispersion for benchmark, drip 80% hydrazine hydrate solution of 0-10 μ L, the graphene oxide dispersion after being reduced wherein。
Further, described metal ion is preferably Zn2+,Cd2+,Pb2+Or Hg2+。
Further, in preparation process (3), the porphyrin concentration of aqueous solution of preparation is minimum is 10-6Mol/L, just can monitor the generation process of porphyrin-graphene complex by the characteristic peak of uv-visible absorption spectra Mesoporphyrin。
In preparation process (4), utilize the preparation process of uv-visible absorption spectra monitoring metalloporphyrin-graphene complex, simple, can carry out at ambient temperature。
Compared with prior art, the beneficial effects of the present invention is:
The present invention is without preparing metalloporphyrin under severe conditions, and preparation process is quick, and preparation condition is gentle, provides a kind of new green method for preparing metalloporphyrin-graphene complex。In addition, regulate and control the ability of metal ion embedding porphyrin ring by changing the electronation degree of graphene oxide, the molecular structure of cationic porphyrin, system pH etc., prepared nano-complex is that a class has the new material of important using value in fields such as catalysis material, photoelectric material and heavy mental treatments。
Accompanying drawing explanation
Fig. 1 is 3mL1 μM of bromination of graphene oxide (GO) titration four (N-pyridylpropyl) porphyrin (TPPyP) adopting 0.15mg/mL, UV, visible light-the absorption spectrum obtained under different GO additions, in figure, Far Left is from below to up, GO addition is stepped up, wherein, abscissa represents wavelength, and vertical coordinate represents absorbance。
Fig. 2 is the maximum absorption band wavelength change (Δ λ) the variation relation curve with addition GO volume, and abscissa represents the addition volume of GO, and vertical coordinate represents maximum absorption band wavelength change。
Fig. 3 is (1) pure TPPyP aqueous solution, (2) TPPyP/GO with three kinds of complex, (3) TPPyP/CCG-1, (4) UV, visible light of TPPyP/CCG-2-absorption spectrum correlation curve, wherein, abscissa represents wavelength, vertical coordinate represents absorbance, Fig. 4 is (2) TPPyP/GO of three kinds of complex, (3) TPPyP/CCG-1, (4) Δ λ comparison diagram when TPPyP/CCG-2 reaches stable, abscissa represents that material is numbered, and vertical coordinate represents maximum absorption band wavelength change when reaching stable。
Fig. 5 be TPPyP, TPPyP/CCG-2, TPPyP/GO and TPPyP/CCG-1 respectively with Zn2+Maximum absorption wavelength (Δ λ) the time dependent graph of a relation of the time dependent uv-visible absorption spectra of mechanism, abscissa representing time, vertical coordinate represents maximum absorption band wavelength change。
Fig. 6 be TPPyP, TPPyP/GO, TPPyP/CCG-1 and TPPyP/CCG-2 respectively with Pb2+,Ca2+,Cd2+,Cu2+,Fe2+,Hg2+,K+,Mg2+,Mn2+,Ni2+,Zn2+Characteristic peak red shift (Δ λ) comparison diagram after Action of Metal Ions, abscissa represents that material is numbered, and vertical coordinate represents maximum absorption band wavelength change。
Fig. 7 is (A) CCG-2, (B) TPPyP/CCG-2, (C) TPPyP-Zn2+Atomic force microscope (AFM) phenogram of/CCG-2 complex, abscissa represents the spacing of white straight line starting point to the end in figure, and vertical coordinate is the height distribution on the indicated straight line of White curves。
Fig. 8 is (A) CCG-2, (B) TPPyP-Zn2+/ CCG-2 composite is degraded paranitrophenol versus time curve under visible ray shines, and abscissa represents degradation time, and vertical coordinate represents degradation rate。
Fig. 9 is that (A) TPPyP-Zn2+/CCG, (B) TPPyP/CCG, (C) TPPyP composite are at the photoelectricity flow graph of the visible light part (λ > 400nm) of xenon lamp, abscissa representing time, vertical coordinate represents current intensity。
Detailed description of the invention
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail。
Embodiment 1
Take bromination four (N-pyridylpropyl) porphyrin (TPPyP) the drying solid powder by classical Alder-longer method synthesis, prepare TPPyP aqueous solution；Prepare graphene oxide (GO), ultrasonic disperse prepares into the GO aqueous dispersions of 0.15mg/mL, measure 40mL, add 28% ammonia 72 μ L, 80% hydrazine hydrate 1.8 μ L (or 7.5 μ L), 95 DEG C of reaction 1h, are cooled to room temperature, are respectively designated as GO, CCG-1, CCG-2 by reducing degree difference after reaction。Monitored the preparation process of complex by uv-visible absorption spectra, test instrunment is ShimadzuUV-2501PC uv-visible absorption spectra instrument。
Result is as shown in Figure 1, the GO aqueous dispersions of 0.15mg/mL is added under room temperature in 1 μM of TPPyP aqueous solution, the porphyrin characteristic peak (Soret band) being positioned at 423nm is gradually lowered, along with being gradually increased of GO addition, the red shift gradually of the characteristic peak of complex solution, when the amount of GO is 50 μ L, maximum absorption wavelength reaches to stabilize to 435nm (Δ λ=13nm), obtains TPPyP/GO complex。Fig. 2 is that maximum absorption band wavelength change (Δ λ) is with the variation relation curve adding GO volume。
Prepare TPPyP/CCG-1, TPPyP/CCG-2 complex respectively by similar approach, result is as shown in Figure 3。As can be seen from the figure, from sample TPPyP/GO to TPPyP/CCG-2, increase along with graphene oxide reducing degree, red shift is all there is with porphyrin feature Soret with corresponding absworption peak in TPPyP at 423nm place, the formation of complex is can determine whether by reaching stable Δ λ, characteristic peak maximum movement respectively 24nm and 32nm, this shows to there occurs effective non-covalent self assembly recombination process between porphyrin and three kinds of Graphenes。Δ λ comparison diagram when Fig. 4 is reach stable。
Embodiment 2
Prepare three kinds of complex (GO/TPPyP, TPPyP/CCG-1, TPPyP/CCG-2) by step in embodiment 1, then dropping concentration is 2 μMs of configuration metal ions Zn respectively2+Aqueous solution, makes concentration proportioning reach 1:2, and under room temperature, mixing stands, and is monitored the change of characteristic absorption peak before and after complex and metallic ion coordination by uv-visible absorption spectra。
Result is as it is shown in figure 5, with Zn2+For exemplary ion, confirm the ultraviolet-visible absorption spectroscopy of it and GO/TPPyP, TPPyP/CCG-1 and TPPyP/CCG-2 interaction different time。Owing under usual conditions, Porphyrin Molecule is higher with the complexation process kinetics energy barrier of metal ion, it is necessary to realize coordination by heating or other auxiliary reagents。Such as Fig. 5, pure TPPyP and Zn under room temperature2+Being difficult to direct coordination, after mixing 48h, characteristic peak has not yet to see apparent motion, it is necessary to heating condition or long-time back flow reaction could occur。But, other the three kinds TPPyP molecules being compounded with Graphene and Zn2+Can at room temperature (25 degrees Celsius) occurring substantially to interact, show as complex Soret band and extend in time red shift occurs gradually, this illustrates that metal ion enters porphyrin ring and there occurs coordination with complex。Comparative result is it can be seen that namely TPPyP/GO reaches stable at about 80min, and red shift 24nm；TPPyP/CCG-1 (40min), faster, and red shift becomes apparent from (respectively 37nm, 47nm) to TPPyP/CCG-2 (25min) speed of action。Therefore, the above results illustrates: in the scope that we study, along with the increase of the reducing degree of graphene oxide, complex and Zn2+In conjunction with speed accelerate。This also illustrates that the graphene oxide utilizing gradient to reduce can regulate and control the planarization in various degree of TPPyP molecule, effective tuning TPPyP and Zn2+The coordination ability of ion, thus successfully realizing the Green synthesis of metalloporphyrin-graphene nanocomposite material under room temperature condition。
Embodiment 3
Prepare complex GO/TPPyP, TPPyP/CCG-1, TPPyP/CCG-2 by step in embodiment 1, then drip other metal ion Pb respectively2+,Ca2+,Cd2+,Cu2+,Fe2+,Hg2+,K+,Mg2+,Mn2+,Ni2+, compare figure with the characteristic peak red shift (Δ λ) of uv-visible absorption spectra。
Result as shown in Figure 6, result show by three kinds of complex GO/TPPyP, TPPyP/CCG-1, TPPyP/CCG-2 respectively with Pb2+,Ca2+,Cd2+,Cu2+,Fe2+,Hg2+,K+,Mg2+,Mn2+,Ni+,Zn2+11 metal ion species interact, and contrast with TPPyP simultaneously, the situation of movement that after comparing porphyrin and metal-complexing, Soret is with。Complex GO/TPPyP is to Cd as shown in Figure 6A2+、Hg2+、Zn2+There is obvious response；Complex TPPyP/CCG-1 is to Pb2+,Cd2+,Hg2+,Mn2+,Zn2+All there is stronger interaction, such as Fig. 6 B；For complex TPPyP/CCG-2, Cd2+、Zn2+Response relatively strong, Pb2+、Hg2+Response die down, the response of other ion is also slightly strengthened, such as Fig. 6 C。Therefore, this result further illustrates us and the graphene oxide that gradient is reduced can be utilized to cause the planarization in various degree of TPPyP molecule, the coordination ability of effective tuning TPPyP and different metal ion, thus successfully realizing the Green synthesis of series metal porphyrin-graphene nanocomposite material under room temperature condition。
Embodiment 4
With (A) CCG-2, (B) TPPyP/CCG-2, (C) TPPyP-Zn of preparation in above-described embodiment 22+/ CCG-2 is pattern and the thickness distribution of representative sample test graphene nanocomposite material sample。
The instrument of concrete test is: BrukerDimensionPT atomic force microscope, and test substrate is the mica sheet of new splitting, and test temperature is 25 DEG C。As shown in Figure 7, result shows: the thickness of the pure Graphene of monolithic (CCG-2) is about 1.3nm, the thickness of the surface recombination graphene complex of porphyrin (TPPyP/CCG-2) is about 5.1nm, it is thus identified that Porphyrin Molecule is in the non-covalent self assembly on CCG surface；Complex TPPyP-Zn2+The thickness of/CCG-2 is about 4.8nm, Zn2+Inside embedding porphyrin ring, further increasing the planarization degree of porphyrin, thickness slightly reduces, and also confirms to embedded in Zn2+TPPyP Porphyrin Molecule remain in CCG surface, define stable ternary graphene composite material at normal temperatures。
Embodiment 5
Complex TPPyP-Zn is prepared by step in embodiment 22+/ CCG-2 and CCG-2, respectively Solar Photocatalytic Degradation of P-nitrophenol (4-NP)。The 4-NP of 250 μ L is added in 25mL complex catalyst, first dark absorption stirring 20min in light protected environment, then at visible light part (λ > 400nm) photocatalytic degradation of xenon lamp, sample every 20min, add the NaOH solution of 20 μ L0.2M afterwards, utilize the absorbance changing value that uv-visible absorption spectra instrument detects the characteristic peak being positioned at 400nm place 4-NP to calculate its degradation efficiency。
Result as shown in Figure 8, complex TPPyP-Zn2+The degradation efficiency of 4-NP is substantially higher in CCG by/CCG-2, has a good application prospect in photocatalytic degradation phenol wastewater field。
Embodiment 6
Complex (A) TPPyP-Zn is prepared by step in embodiment 22+/ CCG-2, (B) TPPyP/CCG-2, (C) TPPyP test the photoelectric properties of graphene nanocomposite material。
The present embodiment adopts three-electrode system, be reference electrode, platinum electrode by complex drop coating to ITO surface preparation work electrode, calomel electrode is that light source is the visible light part (λ > 400nm) at xenon lamp, at the Na2SO of 0.1M to electrode3Electrolyte solution is tested the photoelectric properties of graphene nanocomposite material。
Result is as it is shown in figure 9, complex (A) TPPyP-Zn2+The photoelectric current of/CCG-2 apparently higher than (B) TPPyP/CCG, (C) TPPyP, to have potential using value in field of photovoltaic materials。
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, in the spirit and scope of the claims of the present invention, and any amendment made to the present invention and change, both fall within protection scope of the present invention。
Claims (6)
1. metalloporphyrin-graphene nanocomposite material, its general structure is as follows:
Wherein substituent R is CH3,CH2CH3,(CH2)2CH3,(CH2)3CH3,(CH2)4CH3,(CH2)5CH3,(CH2)3OH,CH2COOCH2CH3,CH2C6H5,CH2C6H4CH3And CH2C6H4NO2In one；
Wherein M is Zn2+,Cd2+,Pb2+Or Hg2+。
2. the method preparing metalloporphyrin-graphene nanocomposite material as claimed in claim 1 under room temperature condition, comprises the steps:
(1) configure certain density cationic porphyrin aqueous solution, be added dropwise over the graphene oxide dispersion of gradient reduction wherein, monitored by uv-visible absorption spectra, when just reaching stable red shift, obtain porphyrin-graphene complex；
(2) in above-mentioned porphyrin-graphene complex dispersion liquid, certain density aqueous metallic ions is dripped, porphyrin in complex is acted under room temperature or room temperature with metal ion, monitored by uv-visible absorption spectra, when reaching stable red shift, namely obtain metalloporphyrin-graphene nanocomposite material。
3. the method preparing metalloporphyrin-graphene nanocomposite material under room temperature condition as claimed in claim 2, described cationic porphyrin, recycle the alkylated reaction synthesis of N after synthesizing four pyridylporphyrins by Alder-longer method or directly buy；The concentration of described cationic porphyrin solution is 1～100 μm of ol/L。
4. the method preparing metalloporphyrin-graphene nanocomposite material under room temperature condition as claimed in claim 2, described gradient reduction is particularly as follows: with 40mL, 0.15mg/mL graphene oxide dispersion is benchmark, drip 80% hydrazine hydrate solution of 0-10 μ L, the graphene oxide dispersion after being reduced wherein。
5. the method preparing metalloporphyrin-graphene nanocomposite material under room temperature condition as claimed in claim 2, in step (2), the ratio of porphyrin-graphene complex and the substance withdrawl syndrome of metal ion is 1:1～5。
6. the method preparing metalloporphyrin-graphene nanocomposite material under room temperature condition as claimed in claim 2, described metal ion is Zn2+,Cd2+,Pb2+Or Hg2+。
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