CN102653396B - Highly dispersed graphene sheet composite material regularly modified by metal nanodot and in-situ preparation method - Google Patents
Highly dispersed graphene sheet composite material regularly modified by metal nanodot and in-situ preparation method Download PDFInfo
- Publication number
- CN102653396B CN102653396B CN201110049804.7A CN201110049804A CN102653396B CN 102653396 B CN102653396 B CN 102653396B CN 201110049804 A CN201110049804 A CN 201110049804A CN 102653396 B CN102653396 B CN 102653396B
- Authority
- CN
- China
- Prior art keywords
- sulfydryl
- graphene film
- perylene diimide
- modified
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002096 quantum dot Substances 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 title abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002114 nanocomposite Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 10
- 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 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 abstract 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract 1
- -1 2-mercaptoethyl Chemical group 0.000 description 23
- 238000002474 experimental method Methods 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 12
- 239000002082 metal nanoparticle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- BGPLBADTZQXKQC-UHFFFAOYSA-N SC(CC1=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)CCCCCCCCCC Chemical group SC(CC1=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)CCCCCCCCCC BGPLBADTZQXKQC-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Abstract
The invention discloses a highly dispersed graphene sheet composite material regularly modified by a metal nanodot and an in-situ preparation method of the graphene sheet composite material. A metal nanodot-modified graphene sheet nanocomposite material comprises nanographene sheets and a metal nanodot for modifying surfaces of the nanographene sheets. The preparation method comprises the following steps of: self-assembling a sulfydryl-containing perylene bisimide derivative molecule to the surface of a graphene oxide sheet, and introducing sulfydryl; reducing the sulfydryl-modified graphene oxide sheet to obtain a sulfydryl-modified graphene oxide sheet; and adding a positive metal salt, and reducing at a sulfydryl site of the surface of the graphene sheet, and generating the metal nanodot and obtain a metal nanodot-modified graphene sheet nanocomposite material. The metal nanodot-modified graphene sheet nanocomposite material obtained by the invention has the advantages of good aqueous solution dispersibility, excellent electrochemical activity and broad application prospect in the fields, such as nanocatalysis, electrochemical sensing and the like.
Description
Technical field
The present invention relates to mixture and preparation method, relate in particular to graphene film matrix material and in-situ preparation method that a kind of metallic nanodots rule with polymolecularity is modified.
Background technology
Graphene can be produced by batch and low consumption by chemical process (as from graphene oxide reduction) at present.In this method, graphene oxide can obtain by graphite crystal is oxidized to peel off, then by after reductive agent, heat, electrochemical reaction reduction, can obtain Graphene (i.e. the graphene oxide of reduction).The two-dimension plane structure of Graphene uniqueness and outstanding electricity, optics, mechanics and chemical property make it become the atomic scale template that a class has the structure novel graphite thiazolinyl nano composite material of potentiality.Such as, after graphene film is modified by metal nanoparticle, its intrinsic various types of properties can be by appropriate regulation to adapt to it in the application in catalysis, energy generation and storage, photoelectronics, sensor field.2008, the graphene film of being modified by golden nanometer particle was by reported first.Subsequently, its photoelectric property is reported and studied to the several pieces of articles about grapheme modified of metal nanoparticle in succession.
Although the graphene film mixture that metal nanoparticle is modified has been obtained certain progress so far, to modified metal size of particles, homogeneity, density, modify the aspects such as the dispersiveness of mixture afterwards and performance and still have huge challenge.A large amount of oxy radicals on graphene oxide surface make graphene oxide in the aqueous solution, have good solvability, and the reaction site of surface chemical modification can be provided.Yet for having the Graphene of high transformation property, graphene oxide is isolator.And the oxy radical of random distribution can cause the random distribution of the metallics in chemically modified.After graphene oxide chemical reduction, can reply significantly conductivity, but but the gathering that can produce graphene film because of pi-pi accumulation and hydrophobic interaction declines the dispersiveness in solution.With regard to being difficult to, continue again the graphene film of monolithic to modify like this.Therefore, the graphene film that the metal nanoparticle of most of report is modified, all in state of aggregation, cannot be adapted to the requirement of types of applications.
Self-assembly is a kind of method of effective structure metal-graphite alkene mixture.In the method, a kind of suitable link molecule (such as organic molecule, DNA, protein) is used to link metal nanoparticle and graphene film.This method is normally linked to previously prepared good metal nanoparticle on graphene film, yet generate metal nanoparticle for original position on graphene film, but cannot effectively control its size, systematicness, density.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the graphene film matrix material and the in-situ preparation method that provide a kind of metallic nanodots rule with polymolecularity to modify.
The graphene film matrix material with the metallic nanodots rule modification of polymolecularity is comprised of graphene film and the metallic nanodots that is modified at graphene film surface, between metallic nanodots and graphene film, by containing sulfydryl perylene diimide derivative molecular, be connected, wherein: the particle diameter of metallic nanodots is 1～3nm, the plane of graphene film is that hundreds of square nanometers are to number square micron.
The described sulfydryl perylene diimide derivative molecular molecular structural formula that contains is:
N is the length of alkyl chain between sub-acid amides and sulfydryl, n=2 or 12.
The described preparation method's who contains sulfydryl perylene diimide derivative molecular step is as follows:
1) 1 weight part 3,4,9,10-perylene tetracarboxylic dianhydride, 0.5～1 weight part mercapto-amine quasi-molecule and 1 weight part Glacial acetic acid zinc join in 10～20mL quinoline, under N2 protection 100～150 ℃ of stirring reactions 3～12 hours;
2) reaction soln is joined in the dehydrated alcohol of 500～1000mL and precipitate, filter and collect filter residue, the sodium hydroxide solution washing that filter residue is 5～10% with weight percent concentration again 3～5 times, filtration, until filtrate is colourless;
3) filter residue is neutral to the pH value change of filtrate with deionized water wash, dry in 70 ℃ of vacuum drying ovens, obtains the perylene diimide derivative molecular that contains sulfydryl.
Described metallic nanodots is gold nano point, silver nanoparticle point, platinum nano dot or palladium nano dot.
The step of in-situ preparation method with the graphene film matrix material that the metallic nanodots rule of polymolecularity modifies is as follows:
1) 2.5～5mg contains sulfydryl perylene diimide derivative molecular after 1～2mL deionized water for ultrasonic is dissolved, join 10～20mL0.5mg/mL graphene oxide aqueous solution, ultrasonic 1～3 hour of mixing solutions, 3000～5000rpm is centrifugal to go out after not tolerant and spends the night in 30～60 ℃ of stirrings, the graphene oxide sheet aqueous solution that the perylene diimide derivative molecular that obtains being contained sulfydryl is modified;
2) to 10～20mL, contain and in the graphene oxide sheet aqueous solution that sulfydryl perylene diimide derivative molecular modifies, add the ammonia soln that hydrazine hydrate solution that 7～14 μ L concentration expressed in percentage by weights are 35% and 75～150 μ L concentration expressed in percentage by weights are 28%, rock mixing solutions after 3～5 minutes in 90～100 ℃ of stirring reactions 1～3 hour, the dark solution obtaining is to contain the graphene film aqueous solution that sulfydryl perylene diimide derivative molecular is modified, excessive hydrazine hydrate and contain sulfydryl perylene diimide derivative molecular and remove by 3500～5000 molecular weight dialysis tubings dialysis in product,
3) 1～5mL0.1mg/mL Thiovanic acid joins in the graphene film aqueous solution of 5～25mL thiol molecule modification, under agitation add 0.16～0.8mL10mM aqueous metal salt to continue reaction and spend the night, obtain having the regular graphene film nano composite material aqueous solution of modifying of metallic nanodots of polymolecularity.
The present invention compares with existing technology the beneficial effect having:
1) metallic nanodots, by containing the non-covalent graphene film surface that is linked at of sulfydryl perylene diimide derivative molecular, can not destroy the chemical structure of Graphene, can not reduce its electricity transport property.
2) metallic nanodots evenly distribution of rule on graphene film, nano dot is of a size of 2nm and size is dispersed little.Nano dot can be controlled in the distribution density on graphene film surface.
3) graphene composite material that the metallic nanodots obtaining is modified has dispersiveness good in the aqueous solution, aggregate and precipitate can not occur, and makes the further application of this mixture become possibility.
Accompanying drawing explanation
Fig. 1 is the low range transmission electron microscope photo with the regular graphene film nano composite material of modifying of metallic nanodots of polymolecularity.
Fig. 2 is the high magnification transmission electron microscope photo with the regular graphene film nano composite material of modifying of metallic nanodots of polymolecularity.
Fig. 3 is the high-resolution-ration transmission electric-lens photo with the regular graphene film nano composite material surface gold nano point of modifying of metallic nanodots of polymolecularity.
Fig. 4 (a) is the transmission electron microscope photo of grapheme modified of gold nano point high-density; Fig. 4 (b) is the transmission electron microscope photo of grapheme modified of gold nano point low-density.
Fig. 5 is the C1s X-ray photoelectric subgraph spectrum with the regular graphene film nano composite material of modifying of metallic nanodots of polymolecularity.
Fig. 6 is the Au4f X-ray photoelectric subgraph spectrum with the regular graphene film nano composite material of modifying of metallic nanodots of polymolecularity.
Embodiment
The invention discloses the graphene film matrix material that a kind of metallic nanodots rule with polymolecularity is modified.The preparation method of the graphene film nano composite material that this metallic nanodots rule is modified comprises: contain sulfydryl perylene diimide derivative molecular and self-assemble to graphene oxide sheet surface introducing sulfydryl; By the reduction of the graphene oxide sheet of sulfydryl modification, obtained the graphene film of sulfydryl modification; Add nominal price metal-salt to generate metallic nanodots, the graphene film nano composite material that obtains being modified by metallic nanodots in the Sulfhydryl Groups reduction on graphene film surface.
The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(1) contain sulfydryl perylene diimide derivative molecular N, N '-bis-(preparation method's of 2-mercaptoethyl) perylene diimide step is as follows:
(a) 1 weight part 3,4,9,10-perylene tetracarboxylic dianhydride, 0.5 weight part mercapto-amine quasi-molecule and 1 weight part Glacial acetic acid zinc join in 10mL quinoline, under N2 protection 100 ℃ of stirring reactions 3 hours;
(b) reaction soln is joined in the dehydrated alcohol of 500mL and precipitate, filter and collect filter residue, the sodium hydroxide solution washing that filter residue is 5% with weight percent concentration again 3 times, filtration, until filtrate is colourless;
(c) filter residue is neutral to the pH value change of filtrate with deionized water wash, dry in 70 ℃ of vacuum drying ovens, obtains N, N '-bis-(2-mercaptoethyl) perylene diimide molecule.
(2) N, N '-bis-(preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film:
(a) 2.5mg N, N '-bis-(2-mercaptoethyl) perylene diimide is after dissolve by 1mL deionized water for ultrasonic, join 10mL0.5mg/mL graphene oxide aqueous solution, ultrasonic 1 hour of mixing solutions, 3000rpm is centrifugal to go out after not tolerant and spends the night in 30 ℃ of stirrings, obtain by N N '-bis-(the graphene oxide sheet aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification;
(b) to 10mL N, N '-bis-(add the ammonia soln that hydrazine hydrate solution that 7 μ L concentration expressed in percentage by weights are 35% and 75 μ L concentration expressed in percentage by weights are 28% in the graphene oxide sheet aqueous solution that 2-mercaptoethyl) perylene diimide is modified, rock mixing solutions after 3 minutes in 90 ℃ of stirring reactions 1 hour, the dark solution obtaining is to contain the graphene film aqueous solution that sulfydryl perylene diimide derivative molecular is modified, excessive hydrazine hydrate and contain sulfydryl perylene diimide derivative molecular and remove by 3500 molecular weight dialysis tubings dialysis in product;
(3) preparation of grapheme modified of gold nano point:
1mL0.1mg/mL Thiovanic acid joins 5mL N, N '-bis-are (in the graphene film aqueous solution that 2-mercaptoethyl) perylene diimide is modified, under agitation add 0.16mL10mM aqueous solution of chloraurate to continue reaction and spend the night, transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of gold nano point of polymolecularity.
Embodiment 2:
(1) contain sulfydryl perylene diimide derivative molecular N, N '-bis-(preparation method's of 2-mercaptoethyl) perylene diimide step is as follows:
A) 1 weight part 3,4,9,10-perylene tetracarboxylic dianhydride, 1 weight part 2-MEA and 1 weight part Glacial acetic acid zinc join in 20mL quinoline, under N2 protection 150 ℃ of stirring reactions 12 hours;
B) reaction soln is joined in the dehydrated alcohol of 1000mL and precipitate, filter and collect filter residue, the sodium hydroxide solution washing that filter residue is 10% with weight percent concentration again 5 times, filtration, until filtrate is colourless;
C) filter residue is neutral to the pH value change of filtrate with deionized water wash, dry in 70 ℃ of vacuum drying ovens, obtains N, N '-bis-(2-mercaptoethyl) perylene diimide molecule.
(2) N, N '-bis-(preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film:
A) 5mgN, N '-bis-(2-mercaptoethyl) perylene diimide is after dissolve by 2mL deionized water for ultrasonic, join 20mL0.5mg/mL graphene oxide aqueous solution, ultrasonic 3 hours of mixing solutions, 5000rpm is centrifugal to go out after not tolerant and spends the night in 60 ℃ of stirrings, obtain by N N '-bis-(the graphene oxide sheet aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification;
B) to 20mL N, N '-bis-(add the ammonia soln that hydrazine hydrate solution that 14 μ L concentration expressed in percentage by weights are 35% and 150 μ L concentration expressed in percentage by weights are 28% in the graphene oxide sheet aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification, rock mixing solutions after 5 minutes in 100 ℃ of stirring reactions 3 hours, the dark solution obtaining is N, N '-bis-(the graphene film aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification, excessive hydrazine hydrate and contain sulfydryl perylene diimide derivative molecular and remove by 5000 molecular weight dialysis tubings dialysis in product;
(3) preparation of grapheme modified of gold nano point:
5mL0.1mg/mL Thiovanic acid joins 25mL N, N '-bis-are (in the graphene film aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification, under agitation add 0.8mL10mM aqueous solution of chloraurate to continue reaction and spend the night, transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of gold nano point of polymolecularity.
Embodiment 3:
(1) N that contains sulfydryl, N '-bis-(preparation method's of 2-sulfydryl dodecyl) perylene diimide step is as follows:
Except raw material replaces Thiovanic acid with sulfydryl amino dodecane, other experimental procedure is with embodiment 1.
(2) N, N '-bis-(the preparation of 2-sulfydryl dodecyl) perylene diimide molecular modification graphene film: except reaction raw materials N, (2-sulfydryl dodecyl) perylene diimide replaces N to N '-bis-, and (outside 2-mercaptoethyl) perylene diimide, experimental procedure is with embodiment 1 for N '-bis-.
(3) preparation of grapheme modified of gold nano point: experimental procedure is with embodiment 1.Transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of gold nano point of polymolecularity.
Embodiment 4:
(1) N that contains sulfydryl, the N '-bis-(preparation method's of 2-sulfydryl dodecyl) perylene diimide step: except raw material replaces Thiovanic acid with sulfydryl amino dodecane, other experimental procedure is with embodiment 2.
(2) N, N '-bis-(the preparation of 2-sulfydryl dodecyl) perylene diimide molecular modification graphene film: except reaction raw materials N, (2-sulfydryl dodecyl) perylene diimide replaces N to N '-bis-, and (outside 2-mercaptoethyl) perylene diimide, experimental procedure is with embodiment 2 for N '-bis-.
(3) preparation of grapheme modified of gold nano point: experimental procedure is with embodiment 2.Transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of gold nano point of polymolecularity.
Embodiment 5:
(1) contain sulfydryl perylene diimide derivative N, the N '-bis-(preparation of 2-mercaptoethyl) perylene diimide: experimental procedure is with embodiment 1.
(2) N, the N '-bis-(preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film: experimental procedure is with embodiment 1.
(3) preparation of grapheme modified of silver nanoparticle point:
Except reaction raw materials metal-salt is Silver Nitrate, other experimental procedures are with embodiment 1, and transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of silver nanoparticle point of polymolecularity.
Embodiment 6:
(1) contain sulfydryl perylene diimide derivative N, the N '-bis-(preparation of 2-mercaptoethyl) perylene diimide: experimental procedure is with embodiment 1.
(2) N, the N '-bis-(preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film: experimental procedure is with embodiment 1.
(3) preparation of grapheme modified of platinum nano dot:
Except reaction raw materials metal-salt is platinum nitrate, other experimental procedures are with embodiment 1, and transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of platinum nano dot of polymolecularity.
Embodiment 7:
(1) contain sulfydryl perylene diimide derivative N, the N '-bis-(preparation of 2-mercaptoethyl) perylene diimide: experimental procedure is with embodiment 1.
(2) N, the N '-bis-(preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film: experimental procedure is with embodiment 1.
(3) preparation of grapheme modified of palladium nano dot:
Except reaction raw materials metal-salt is Palladous nitrate, other experimental procedures are with embodiment 1, and transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of palladium nano dot of polymolecularity.
Claims (1)
1. the graphene film matrix material that the metallic nanodots rule with polymolecularity is modified, it is characterized in that being formed by graphene film and the metallic nanodots that is modified at graphene film surface, between metallic nanodots and graphene film, by containing sulfydryl perylene diimide derivative molecular, be connected, wherein: the particle diameter of metallic nanodots is 1～3 nm, the plane of graphene film is that hundreds of square nanometers are to number square micron;
The described sulfydryl perylene diimide derivative molecular molecular structural formula that contains is:
N is the length of alkyl chain between sub-acid amides and sulfydryl, n=2 or 12.
2.the graphene film matrix material that a kind of metallic nanodots rule with polymolecularity according to claim 1 is modified, is characterized in that the described preparation method who contains sulfydryl perylene diimide derivative molecular comprises the following steps:
1) 1 weight part 3,4,9,10-perylene tetracarboxylic dianhydride, 0.5～1 weight part mercapto-amine quasi-molecule and 1 weight part Glacial acetic acid zinc join in 10～20 mL quinoline, in N
2under protection 100～150 ℃ of stirring reactions 3～12 hours;
2) reaction soln is joined in the dehydrated alcohol of 500～1000 mL and precipitate, filter and collect filter residue, the sodium hydroxide solution washing that filter residue is 5～10% with weight percent concentration again 3～5 times, filtration, until filtrate is colourless;
3) filter residue is neutral to the pH value change of filtrate with deionized water wash, dry in 70 ℃ of vacuum drying ovens, obtains the perylene diimide derivative molecular that contains sulfydryl.
3.a graphene film matrix material according to claim 1 with the metallic nanodots rule modification of polymolecularity, is characterized in that described metallic nanodots is gold nano point, silver nanoparticle point, platinum nano dot or palladium nano dot.
4.an in-situ preparation method according to claim 1 with the regular graphene film matrix material of modifying of metallic nanodots of polymolecularity, is characterized in that its step is as follows:
1) 2.5～5 mg contain sulfydryl perylene diimide derivative molecular after 1～2 mL deionized water for ultrasonic is dissolved, join 10～20 mL 0.5 mg/mL graphene oxide aqueous solution, ultrasonic 1～3 hour of mixing solutions, 3000～5000 rpm are centrifugal to go out after insolubles and spends the night in 30～60 ℃ of stirrings, the graphene oxide sheet aqueous solution that obtains being contained sulfydryl perylene diimide derivative molecular and modify;
2) in the graphene oxide sheet aqueous solution that contains the modification of sulfydryl perylene diimide derivative molecular to 10～20 mL, adding 7～14 μ L concentration expressed in percentage by weights is the hydrazine hydrate solution of 35 % and the ammonia soln that 75～150 μ L concentration expressed in percentage by weights are 28%, rock mixing solutions after 3～5 minutes in 90～100 ℃ of stirring reactions 1～3 hour, the dark solution obtaining is to contain the graphene film aqueous solution that sulfydryl perylene diimide derivative molecular is modified, excessive hydrazine hydrate and contain sulfydryl perylene diimide derivative molecular and remove by 3500～5000 molecular weight dialysis tubings dialysis in product,
3) 1～5 mL 0.1 mg/mL Thiovanic acid joins 5～25 mL and contains in the graphene film aqueous solution that sulfydryl perylene diimide derivative molecular modifies, under agitation add 0.16～0.8 mL 10 mM aqueous metal salts to continue reaction and spend the night, obtain having the regular graphene film nano composite material aqueous solution of modifying of metallic nanodots of polymolecularity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110049804.7A CN102653396B (en) | 2011-03-02 | 2011-03-02 | Highly dispersed graphene sheet composite material regularly modified by metal nanodot and in-situ preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110049804.7A CN102653396B (en) | 2011-03-02 | 2011-03-02 | Highly dispersed graphene sheet composite material regularly modified by metal nanodot and in-situ preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102653396A CN102653396A (en) | 2012-09-05 |
| CN102653396B true CN102653396B (en) | 2014-02-26 |
Family
ID=46729147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110049804.7A Expired - Fee Related CN102653396B (en) | 2011-03-02 | 2011-03-02 | Highly dispersed graphene sheet composite material regularly modified by metal nanodot and in-situ preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102653396B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923700B (en) * | 2012-11-30 | 2015-05-20 | 南京大学 | Preparation method of thiol-modified graphene |
| CN104569052B (en) * | 2014-12-17 | 2017-02-22 | 东南大学 | Method for preparing graphene oxide sensor |
| CN108637270B (en) * | 2018-05-02 | 2021-09-21 | 戚明海 | Method for preparing metal nanoparticles by using graphene oxide as template |
| CN108865115A (en) * | 2018-06-01 | 2018-11-23 | 湖南国盛石墨科技有限公司 | A kind of photoelectric material preparation method of acid imide containing graphene and its derivative |
| CN110229153B (en) * | 2019-06-24 | 2022-08-19 | 赣南师范大学 | Intercalation molecule, preparation method thereof and two-dimensional nanocomposite |
| CN110274936B (en) * | 2019-07-09 | 2021-10-26 | 济南大学 | Organic-inorganic composite film for detecting triethylamine and gas sensor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110186789A1 (en) * | 2008-05-22 | 2011-08-04 | The University Of North Carolina At Chapel Hill | Synthesis of graphene sheets and nanoparticle composites comprising same |
| CN101913598B (en) * | 2010-08-06 | 2012-11-21 | 浙江大学 | Method for preparing graphene membrane |
| CN101913592A (en) * | 2010-08-10 | 2010-12-15 | 浙江大学 | Covalent functionalization graphene and preparation method thereof |
-
2011
- 2011-03-02 CN CN201110049804.7A patent/CN102653396B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102653396A (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102653396B (en) | Highly dispersed graphene sheet composite material regularly modified by metal nanodot and in-situ preparation method | |
| Huang et al. | Facile synthesis and one-dimensional assembly of cyclodextrin-capped gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering | |
| Dong et al. | A review on WO3 based gas sensors: Morphology control and enhanced sensing properties | |
| Paredes et al. | Impact of covalent functionalization on the aqueous processability, catalytic activity, and biocompatibility of chemically exfoliated MoS2 nanosheets | |
| Ghiyasiyan-Arani et al. | Enhanced photodegradation of dye in waste water using iron vanadate nanocomposite; ultrasound-assisted preparation and characterization | |
| Suárez-Cerda et al. | A green synthesis of copper nanoparticles using native cyclodextrins as stabilizing agents | |
| Yang et al. | Additive-free synthesis of In2O3 cubes embedded into graphene sheets and their enhanced NO2 sensing performance at room temperature | |
| Mohamed et al. | Laminating of chemically modified silan based nanosols for advanced functionalization of cotton textiles | |
| Shang et al. | Improving dispersion stability of hydrochloric acid hydrolyzed cellulose nano-crystals | |
| Chen et al. | Simple solution-phase synthesis of soluble CdS and CdSe nanorods | |
| Wang et al. | Controlled synthesis of Ag2S, Ag2Se, and Ag nanofibers by using a general sacrificial template and their application in electronic device fabrication | |
| Fei et al. | Solubilization, purification and functionalization of carbon nanotubes using polyoxometalate | |
| Guo et al. | Preparation of a novel nanocomposite of polyaniline core decorated with anatase-TiO2 nanoparticles in ionic liquid/water microemulsion | |
| Wang et al. | Fabrication of perylene imide-modified NH2-UiO-66 for enhanced visible-light photocatalytic degradation of tetracycline | |
| Kumar | Mixed phase lamellar titania-titanate anchored with Ag2O and polypyrrole for enhanced adsorption and photocatalytic activity | |
| Kozhummal et al. | Antisolvent crystallization approach to construction of CuI superstructures with defined geometries | |
| Dursun et al. | PMN-PT nanoparticle/SnO2 nanofiber heterostructures: Enhanced photocatalytic degradation performance by ultrasonic wave induced piezoelectric field | |
| Junaidi et al. | The roles of polyvinyl alcohol (PVA) as the capping agent on the polyol method for synthesizing silver nanowires | |
| Basavaraja et al. | Characterization and temperature-dependent conductivity of polyaniline nanocomposites encapsulating gold nanoparticles on the surface of carboxymethyl cellulose | |
| Jorge et al. | Preparation and characterization of polyaniline nanocomposites with graphene oxide-zinc oxide hybrids in different morphologies | |
| Mitra et al. | Efficacy of highly water-dispersed fabricated nano ZnO against clinically isolated bacterial strains | |
| Zhao et al. | Facile synthesis of low crystalline BiOCl-based thermally-responsive photocatalyst with enhanced catalytic performance for photodegrading rhodamine B solution | |
| Fu et al. | One-dimensional magnetic nanocomposites with attapulgites as templates: growth, formation mechanism and magnetic alignment | |
| CN101538736A (en) | Dendritic golden nanophase material and preparation method thereof | |
| Alshammari et al. | Ultrasonic-assisted synthesis and characterization of chitosan-graft-substituted polyanilines: promise bio-based nanoparticles for dye removal and bacterial disinfection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140226 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |